Colored curable composition, color filter and method of producing color filter, solid-state image sensor and liquid crystal display device

ABSTRACT

The present invention provides a colored curable composition including a phthalocyanine pigment, a dioxazine pigment, a dye, a polymerization initiator, a polymerizable compound and a solvent; and a colored curable composition including a phthalocyanine pigment, a dye multimer having a polymerizable group and a group derived from a dipyrromethene dye, a polymerization initiator, a polymerizable compound and a solvent.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority under 35 USC 119 from Japanese PatentApplication No. 2010-043529 filed Feb. 26, 2010 and Japanese PatentApplication No. 2010-043530 filed Feb. 26, 2010, the disclosure of whichis incorporated by reference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a colored curable composition, a colorfilter and a method of producing a color filter, a solid-state imagesensor and a liquid crystal display device.

2. Description of the Related Art

As a method of producing a color filter used in liquid crystal displaydevices (LCDs) or solid-state image sensors (CCD or CMOS image sensors),a pigment dispersion method has been widely known.

A pigment dispersion method is a method of producing a color filter byphotolithography using a colored photosensitive composition in which apigment is dispersed in various kinds of photosensitive composition.This method, in which patterning is performed by photolithography, isknown to be suitable for producing large-sized, high-definition colorfilters with high positional accuracy. When producing color filters by apigment dispersion method, a coating film is formed by applying aphotosensitive composition on a glass support with a spin coater or aroll coater, exposing the coating film to light and developing the sameto form color pixels. A color filter is thus obtained by repeating theseprocesses a number of times according to the number of colors used inthe color filter.

One exemplary colored photosensitive composition in which a pigment isused is a blue colored composition for color filters in which aphthalocyanine pigment is included, as described in Japanese PatentApplication Laid-Open (JP-A) No. 2001-33616.

When producing display devices, such as liquid crystal display devicesor solid-state image sensors, by forming a color filter using a pigment,a pigment having a small particle size is desired in view of improvingcontrast. Problems in contrast are caused by light scattering due to apigment or rotation of the polarizing axis by double refraction or thelike. When micronization of a pigment is not sufficient, light isscattered or absorbed by the pigment, whereby light transmissivity isdecreased and contrast is lowered and, moreover, curing sensitivity atthe time of pattern exposure may be decreased.

In particular, in the field of color filters for solid-state imagesensors, in which even higher definition has been required in recentyears, further improvements in resolution has been difficult in aconventional pigment dispersion system, i.e., there are problems in thatunevenness in color may occur due to coarse pigment particles, and thelike. As a result, a pigment dispersion system is not suitable forapplications that require a highly fine pattern for solid-state imagesensors with a pixel size of from 1.5 to 3.0 μm square.

In response to such circumstances, techniques in which a dye is usedinstead of a pigment have been proposed. However, dyes have problemssuch as light resistance and heat resistance being inferior comparedwith pigments, which may cause problems in performance of color filters.There is also a problem in that a dye may precipitate due to its lowsolubility with respect to a photosensitive composition, and poorstability with time in the form of a liquid formulation or a coatingfilm.

In view of such problems, a colored curable composition has beenproposed in which a dye including a dipyrromethene compound and aphthalocyanine dye are used in combination, the composition exhibitingsuperior storage stability and being capable of forming a color filterthat exhibits a high light resistance (see, for example, JP-A No.2008-292970).

Further, a colored curable composition, in which a dye and a pigment arecombined, is known (see, for example, United States Patent ApplicationPublication No. 2008/0171271).

SUMMARY OF THE INVENTION

A first aspect of the invention provides a colored curable compositioncontaining a phthalocyanine pigment, a dioxazine pigment, a dye, apolymerization initiator, a polymerizable compound, and a solvent.

A second aspect of the invention provides a colored curable compositioncomprising a phthalocyanine pigment, a dye multimer having apolymerizable group and a group derived from a dipyrromethene dye, apolymerization initiator, a polymerizable compound, and a solvent.

<First Aspect>

The first aspect of the present invention provides a colored curablecomposition containing a phthalocyanine pigment, a dioxazine pigment, adye, a polymerization initiator, a polymerizable compound, and asolvent.

As described above, it is known that a colored curable composition inwhich a dye is used provides effects such as formation of a color filterthat exhibits superior light fastness etc. by selecting a suitable dye.However, it is also true that these effects need to be further enhancedin order to realize even higher fineness or improved performances ofcolor filters.

The first aspect of the present invention has been made in view of theabove circumstances, and an object thereof is to provide a coloredcurable composition capable of forming a colored cured film that exhibitsuperior light fastness.

A further object of the first aspect of the present invention is toprovide a color filter that exhibits superior light fastness and amethod for producing the color filter; and a solid-state image sensorand a liquid crystal display device including the color filter.

According to the first aspect of the invention, a colored curablecomposition capable of forming a colored cured film that exhibitssuperior light fastness can be provided.

According to the first aspect of the invention, a color filter thatexhibits superior light fastness and a method of producing the same, anda solid-state image sensor and a liquid crystal display device includingthe color filter can be provided.

<Colored Curable Composition>

First, the colored curable composition of the first aspect of theinvention will be described.

The colored curable composition of the first aspect of the inventionincludes a phthalocyanine pigment, a dioxazine pigment, a dye, apolymerization initiator, a polymerizable compound, and a solvent.

In order to obtain favorable spectroscopic characteristics of a blue orgreen colored cured film (in particular, a blue colored cured film), thecombined use of a phthalocyanine pigment and a dye as a colorant in thecolored curable composition is effective. However, since a dye is proneto decomposition when exposed to light, colored curable compositionscontaining a dye generally exhibits poor light fastness.

In view of the above, the present inventors have made extensive studiesand, as a result, arrived at the invention based on the findings thatdecomposition of a dye can be suppressed and light fastness of a bluecured film can be improved when a dioxazine pigment is used in additionto a phthalocyanine pigment and a dye as a colorant in the coloredcurable composition.

Accordingly, when the colored curable composition of the first aspect ofthe invention is used, a colored cured film that exhibits improved lightfastness can be obtained.

The reason why decomposition of a dye is suppressed is presumed to bethat light that allows the dye to decompose is absorbed by the dioxazinepigment. However, the first aspect of the invention is not limited tothis speculation.

Hereinafter, the components of the colored curable composition of thefirst aspect of the invention will be described.

<Phthalocyanine Pigment>

The colored curable composition of the first aspect of the inventioncontains a phthalocyanine pigment.

The phthalocyanine pigment used in the first aspect of the invention isnot particularly limited as long as it is a pigment having aphthalocyanine backbone. The central metal included in thephthalocyanine pigment is not particularly limited and may be any metalas long as it can form a phthalocyanine backbone. Among them, magnesium,titanium, iron, cobalt, nickel, copper, zinc and aluminum are preferablyused as the central metal.

Specific examples of the phthalocyanine pigment used in the first aspectof the invention include C.I. Pigment Blue 15, C.I. Pigment Blue 15:1,C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4,C.I. Pigment Blue 15:5, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16,C.I. Pigment Blue 17:1, C.I. Pigment Blue 75, C.I. Pigment Blue 79, C.I.Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37,chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, aluminumphthalocyanine oxide and zinc phthalocyanine. Among them, C.I. PigmentBlue 15, C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:1 and C.I. PigmentBlue 15:2 are preferable, and C.I. Pigment Blue 15:6 is particularlypreferable in view of light fastness and tinctorial strength.

The content of the phthalocyanine pigment in the colored curablecomposition of the first aspect of the invention is preferably in therange of from 5% by mass to 60% by mass, more preferably from 10% bymass to 60% by mass, and most preferably from 35% by mass to 50% bymass, with respect to the total solid components of the colored curablecomposition, in view of adjusting color hues of a color filter.

<Dioxazine Pigment>

The colored curable composition of the first aspect of the inventionincludes a dioxazine pigment.

Examples of the dioxazine pigment include C.I. Pigment Violet 19, C.I.Pigment Violet 23, C.I. Pigment Violet 32, and C.I. Pigment Violet 37.Among them, C.I. Pigment Violet 23 is preferable.

The content of the dioxazine pigment in the colored curable compositionof the first aspect of the invention is in the range of from 0.1% bymass to 40% by mass, more preferably from 0.1% by mass to 20% by mass,and particularly preferably from 0.3% by mass to 10% by mass, withrespect to the total solid components in the colored curablecomposition.

If the content of the dioxazine pigment is 0.1% by mass or more, it ispossible to more effectively improve the light fastness.

If the content of the dioxazine pigment is 40% by mass or less, it ispossible to more effectively adjust the color hues.

Further, in the colored curable composition of the first aspect of theinvention, the mass ratio of the dioxazine pigment to the dye to bedescribed hereinafter (dioxazine pigment/dye) is preferably in the rangeof from 0.01 to 2.00, more preferably from 0.05 to 1.50, andparticularly preferably from 0.35 to 0.80.

If the mass ratio (dioxazine pigment/dye) is 0.01 or greater, it ispossible to more effectively improve the light fastness.

If the mass ratio (dioxazine pigment/dye) is 2.00 or less, it ispossible to more effectively adjust the color hues.

<Dye>

The colored curable composition of the first aspect of the inventionincludes a dye.

The dye is not particularly limited, and any known dyes that have beenconventionally used in color filters may be used. Examples of such dyesinclude dyes described in JP-A Nos. 64-90403, 64-91102, 1-94301 and6-11614, Japanese Patent Registration No. 2592207, U.S. Pat. Nos.4,808,501, 5,667,920, 505,950 and 5,667,920, JP-A Nos. 5-333207,6-35183, 6-51115 and 6-194828, and the like. Examples of the chemicalstructure of the dye include a pyrazole azo dye, an anilino azo dye, atriphenylmethane dye, an anthraquinone dye, a benzylidene dye, an oxonoldye, a pyrazolotriazole azo dye, a pyridone azo dye, a cyanine dye, aphenothiazine dye, and a pyrrolopyrazole azomethine dye.

Among them, from the viewpoint that the absorption wavelength is closeto that of a dioxazine pigment, a complex including a compoundrepresented by the following formula (I) and a metal atom or a metalcompound (hereinafter, also referred to as a “specific complex”) ispreferable.

(Dipyrromethene Compound)

First, the compound represented by the formula (I) that constitutes thespecific complex (dipyrromethene compound) is described.

In the formula (I), each of R¹ to R⁶ independently represents a hydrogenatom or a substituent, and R⁷ represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group or a heterocyclic group.

It is preferred that R¹ and R⁶ are not bonded to each other to form aring.

Examples of the substituent represented by R¹ to R⁶ in the formula (I)include the following monovalent groups (hereinafter, these monovalentgroups may be collectively referred to as “Substituent R”).

A halogen atom (for example, a fluorine atom, a chlorine atom or abromine atom), an alkyl group (a linear, branched or cyclic alkyl grouphaving preferably 1 to 48 carbon atoms, more preferably 1 to 24 carbonatoms, such as a methyl group, an ethyl group, a propyl group, anisopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a 2-ethylhexyl group, a dodecylgroup, a hexadecyl group, a cyclopropyl group, a cyclopentyl group, acyclohexyl group, a 1-norbornyl group or a 1-adamantyl group), analkenyl group (an alkenyl group having preferably 2 to 48 carbon atoms,more preferably 2 to 18 carbon atoms, such as a vinyl group, an allylgroup or a 3-buten-1-yl group), an aryl group (an aryl group havingpreferably 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms,such as a phenyl group or a naphthyl group), a heterocyclic group (aheterocyclic group having preferably 1 to 32 carbon atoms, morepreferably 1 to 18 carbon atoms, such as a 2-thienyl group, a 4-pyridylgroup, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group or abenzotriazol-1-yl group), a silyl group (a silyl group having preferably3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as atrimethylsilyl group, a triethylsilyl group, a tributylsilyl group, at-butyldimethylsilyl group or a t-hexyldimethylsilyl group), a hydroxylgroup, a cyano group, a nitro group, an alkoxy group (an alkoxy grouphaving preferably 1 to 48 carbon atoms, more preferably 1 to 24 carbonatoms, such as a methoxy group, an ethoxy group, a 1-butoxy group, a2-butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxygroup, or a cycloalkyloxy group, for example a cyclopentyloxy group or acyclohexyloxy group), an aryloxy group (an aryloxy group havingpreferably 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms,such as a phenoxy group or a 1-naphthoxy group), a heterocyclic oxygroup (a heterocyclic oxy group having preferably 1 to 32 carbon atoms,more preferably 1 to 18 carbon atoms, such as a 1-phenyltetrazole-5-oxygroup or a 2-tetrahydropyranyloxy group), a silyloxy group (a silyloxygroup having preferably 1 to 32 carbon atoms, more preferably 1 to 18carbon atoms, such as a trimethylsilyloxy group, at-butyldimethylsilyloxy group or a diphenylmethylsilyloxy group), anacyloxy group (an acyloxy group having preferably 2 to 48 carbon atoms,more preferably 2 to 24 carbon atoms, such as an acetoxy group, apivaloyloxy group, a benzoyloxy group or a dodecanoyloxy group), analkoxycarbonyloxy group (an alkoxycarbonyloxy group having preferably 2to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as anethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or acycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxygroup), an aryloxycarbonyloxy group (an aryloxycarbonyloxy group havingpreferably 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms,such as a phenoxycarbonyloxy group), a carbamoyloxy group (acarbamoyloxy group having preferably 1 to 48 carbon atoms, morepreferably 1 to 24 carbon atoms, such as an N,N-dimethylcarbamoyloxygroup, an N-butylcarbamoyloxy group, an N-phenylcarbamoyloxy group or anN-ethyl-N-phenylcarbamoyloxy group), a sulfamoyloxy group (asulfamoyloxy group having preferably 1 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms, such as an N,N-diethylsulfamoyloxygroup or an N-propylsulfamoyloxy group), an alkylsulfonyloxy group (analkylsulfonyloxy group having preferably 1 to 38 carbon atoms, morepreferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group, ahexadecylsulfonyloxy group or a cyclohexylsulfonyloxy group),

an arylsulfonyloxy group (an arylsulfonyloxy group having preferably 6to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as aphenylsulfonyloxy group), an acyl group (an acyl group having preferably1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as aformyl group, an acetyl group, a pivaloyl group, a benzoyl group, atetradecanoyl group or a cyclohexanoyl group), an alkoxycarbonyl group(an alkoxycarbonyl group having preferably 2 to 48 carbon atoms, morepreferably 2 to 24 carbon atoms, such as a methoxycarbonyl group, anethoxycarbonyl group, an octadecyloxycarbonyl group, acyclohexyloxycarbonyl group or a2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), anaryloxycarbonyl group (an aryloxycarbonyl group having preferably 7 to32 carbon atoms, more preferably 7 to 24 carbon atoms, such as aphenoxycarbonyl group), a carbamoyl group (a carbamoyl group havingpreferably 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms,such as a carbamoyl group, an N,N-diethylcarbamoyl group, anN-ethyl-N-octylcarbamoyl group, an N,N-dibutylcarbamoyl group, anN-propylcarbamoyl group, an N-phenylcarbamoyl group, anN-methyl-N-phenylcarbamoyl group or an N,N-dicyclohexylcarbamoyl group),an amino group (an amino group having preferably 32 or less carbonatoms, more preferably 24 or less carbon atoms, such as an amino group,a methylamino group, an N,N-dibutylamino group, a tetradecylamino group,a 2-ethylhexylamino group or a cyclohexylamino group), an anilino group(an anilino group having preferably 6 to 32 carbon atoms, morepreferably 6 to 24 carbon atoms, such as an anilino group or anN-methylanilino group), a heterocyclic amino group (a heterocyclic aminogroup having preferably 1 to 32 carbon atoms, more preferably 1 to 18carbon atoms, such as a 4-pyridylamino group), a carbonamido group (acarbonamido group having preferably 2 to 48 carbon atoms, morepreferably 2 to 24 carbon atoms, such as an acetamido group, a benzamidogroup, a tetradecanamido group, a pivaloylamido group or acyclohexanamido group), an ureido group (an ureido group havingpreferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms,such as an ureido group, an N,N-dimethylureido group or anN-phenylureido group), an imido group (an imido group having preferably36 or less carbon atoms, more preferably 24 or less carbon atoms, suchas an N-succinimido group or an N-phthalimido group), analkoxycarbonylamino group (an alkoxycarbonylamino group havingpreferably 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms,such as a methoxycarbonylamino group, an ethoxycarbonylamino group, at-butoxycarbonylamino group, an octadecyloxycarbonylamino group or acyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (anaryloxycarbonylamino group having preferably 7 to 32 carbon atoms, morepreferably 7 to 24 carbon atoms, such as a phenoxycarbonylamino group),a sulfonamido group (a sulfonamido group having preferably 1 to 48carbon atoms, more preferably 1 to 24 carbon atoms, such as amethanesulfonamido group, a butanesulfonamido group, abenzenesulfonamido group, a hexadecanesulfonamido group or acyclohexanesulfonamido group), a sulfamoylamino group (a sulfamoylaminogroup having preferably 1 to 48 carbon atoms, more preferably 1 to 24carbon atoms, such as an N,N-dipropylsulfamoylamino group or anN-ethyl-N-dodecylsulfamoylamino group), an azo group (an azo grouphaving preferably 1 to 32 carbon atoms, more preferably 1 to 24 carbonatoms, such as a phenylazo group or a 3-pyrazolylazo group),

an alkylthio group (an alkylthio group having preferably 1 to 48 carbonatoms, more preferably 1 to 24 carbon atoms, such as a methylthio group,an ethylthio group, an octylthio group or a cyclohexylthio group), anarylthio group (an arylthio group having preferably 6 to 48 carbonatoms, more preferably 6 to 24 carbon atoms, such as a phenylthiogroup), a heterocyclic thio group (a heterocyclic thio group havingpreferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms,such as a 2-benzothiazolylthio group, a 2-pyridylthio group or a1-phenyltetrazolylthio group), an alkylsulfinyl group (an alkylsulfinylgroup having preferably 1 to 32 carbon atoms, more preferably 1 to 24carbon atoms, such as a dodecanesulfinyl group), an arylsulfinyl group(an arylsulfinyl group having preferably 6 to 32 carbon atoms, morepreferably 6 to 24 carbon atoms, such as a phenylsulfinyl group), analkylsulfonyl group (an alkylsulfonyl group having preferably 1 to 48carbon atoms, more preferably 1 to 24 carbon atoms, such as amethylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, abutylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonylgroup, a hexadecylsulfonyl group, an octylsulfonyl group or acyclohexylsulfonyl group), an arylsulfonyl group (an arylsulfonyl grouphaving preferably 6 to 48 carbon atoms, more preferably 6 to 24 carbonatoms, such as a phenylsulfonyl group or a 1-naphthylsulfonyl group), asulfamoyl group (a sulfamoyl group having preferably 32 or less carbonatoms, more preferably 24 or less carbon atoms, such as a sulfamoylgroup, an N,N-dipropylsulfamoyl group, an N-ethyl-N-dodecylsulfamoylgroup, an N-ethyl-N-phenylsulfamoyl group or an N-cyclohexylsulfamoylgroup), a sulfo group, a phosphonyl group (a phosphonyl group havingpreferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms,such as a phenoxyphosphonyl group, an octyloxyphosphonyl group or aphenylphosphonyl group) and a phosphinoylamino group (a phosphinoylaminogroup having preferably 1 to 32 carbon atoms, more preferably 1 to 24carbon atoms, such as a diethoxyphosphinoylamino group or adioctyloxyphosphinoylamino group).

When the above-mentioned monovalent groups are a group that can befurther substituted, the group may be further substituted by any one ofthe above-mentioned groups. When the monovalent group has two or moresubstituents, these substituents may be the same or different from eachother.

In the formula (I), combinations of R¹ and R², R² and R³, R⁴ and R⁵, andR⁵ and R⁶ may independently bond to each other to form a 5-, 6- or7-membered ring. Examples of the ring formed from the above combinationsinclude saturated or unsaturated rings. Examples of the 5-, 6- or7-membered saturated or unsaturated rings include a pyrrole ring, afuran ring, a thiophene ring, a pyrazole ring, an imidazole ring, atriazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, apiperidine ring, a cyclopentene ring, a cyclohexene ring, a benzenering, a pyridine ring, a pyrazine ring and a pyridazine ring, preferablya benzene ring and a pyridine ring.

When the 5-, 6- or 7-membered ring is a group that can be furthersubstituted, the group may be substituted by any one of the groupsmentioned as Substituent R, and when the ring is substituted by two ormore substituents, these substituents may be the same or different fromeach other.

In the formula (I), when R⁷ represents a halogen atom, an alkyl group,an aryl group or a heterocyclic group, preferable ranges thereof are thesame as the preferable ranges of a halogen atom, an alkyl group, an arylgroup or a heterocyclic group represented by R¹ to R⁶.

Among these groups, R¹ and R⁶ in the formula (I) preferably represent analkylamino group, an arylamino group, a carbonamido group, an ureidogroup, an imido group, an alkoxycarbonylamino group or a sulfonamidogroup, more preferably a carbonamido group, an ureido group, analkoxycarbonylamino group or a sulfonamido group, and particularlypreferably a carbonamido group or an ureido group.

Among these groups, R² and R⁵ in the formula (I) preferably represent analkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, analkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imidogroup or a carbamoylsulfonyl group, more preferably an alkoxycarbonylgroup, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonylgroup, a nitrile group, an imido group or a carbamoylsulfonyl group,still more preferably an alkoxycarbonyl group, an aryloxycarbonyl group,a carbamoyl group, a nitrile group, an imido group or acarbamoylsulfonyl group, and particularly preferably an alkoxycarbonylgroup, an aryloxycarbonyl group or a carbamoyl group.

Among these groups, R³ and R⁴ in the formula (I) preferably represent asubstituted or unsubstituted alkyl group, a substituted or unsubstitutedaryl group, or a substituted or unsubstituted heterocyclic group, morepreferably a substituted or unsubstituted alkyl group, or a substitutedor unsubstituted aryl group.

When R³ and R⁴ in the formula (I) represent an alkyl group, examples ofthe alkyl group preferably include a linear, branched or cyclic,substituted or unsubstituted alkyl group having 1 to 12 carbon atoms,more specifically, for example, a methyl group, an ethyl group, ann-propyl group, an isopropyl group, a cyclopropyl group, an n-butylgroup, an i-butyl group, a t-butyl group, a cyclobutyl group, acyclopentyl group, a cyclohexyl group and a benzyl group, morepreferably a branched or cyclic, substituted or unsubstituted alkylgroup having 1 to 12 carbon atoms, still more specifically, for example,an isopropyl group, a cyclopropyl group, an i-butyl group, a t-butylgroup, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group,even more preferably a secondary or tertiary substituted orunsubstituted alkyl group having 1 to 12 carbon atoms, and morespecifically, for example, an isopropyl group, a cyclopropyl group, ani-butyl group, a t-butyl group, a cyclobutyl group and a cyclohexylgroup.

When R³ and R⁴ in the formula (I) represent an aryl group, examples ofthe aryl group preferably include a substituted or unsubstituted phenylgroup and a substituted or unsubstituted naphthyl group, more preferablya substituted or unsubstituted phenyl group.

When R³ and R⁴ represent a heterocyclic group, examples of theheterocyclic group preferably include a substituted or unsubstituted2-thienyl group, a substituted or unsubstituted 4-pyridyl group, asubstituted or unsubstituted 3-pyridyl group, a substituted orunsubstituted 2-pyridyl group, a substituted or unsubstituted 2-furylgroup, a substituted or unsubstituted 2-pyrimidinyl group, a substitutedor unsubstituted 2-benzothiazolyl group, a substituted or unsubstituted1-imidazolyl group, a substituted or unsubstituted 1-pyrazolyl group anda substituted or unsubstituted benzotriazol-1-yl group, more preferablya substituted or unsubstituted 2-thienyl group, a substituted orunsubstituted 4-pyridyl group, a substituted or unsubstituted 2-furylgroup, a substituted or unsubstituted 2-pyrimidinyl group and asubstituted or unsubstituted 1-pyridyl group.

—Metal Atom or Metal Compound—

Next, a metal atom or a metal compound that constitutes the specificcomplex will be described.

The metal atom or the metal compound used in the invention may be anymetal atom or metal compound as long as it can form a complex, andexamples thereof include divalent metal atoms, divalent metal oxides,divalent metal hydroxides and divalent metal chlorides, for example, Zn,Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe and the like, as wellas metal chlorides including AlCl, InCl, FeCl, TiCl₂, SnCl₂, SiCl₂ andGeCl₂, metal oxides including TiO and VO, and metal hydroxides includingSi(OH)₂.

Among them, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO and VO arepreferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co and VO are morepreferable, and Fe, Zn, Cu, Co and VO (V═O) are most preferable, in viewof stability, spectroscopic properties, heat resistance, light fastness,manufacturability etc. of the complex.

Preferred examples of the complex containing a compound represented bythe formula (I) and a metal atom or a metal compound include a complexthat includes:

a compound represented by the formula (I) in which each of R¹ and R⁶independently represents a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, a silyl group, a hydroxylgroup, a cyano group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, anamino group, an anilino group, a heterocyclic amino group, a carbonamidogroup, an ureido group, an imido group, an alkoxycarbonylamino group, anaryloxycarbonylamino group, a sulfonamido group, an azo group, analkylthio group, an arylthio group, a heterocyclic thio group, analkylsulfonyl group, an arylsulfonyl group or a phosphinoylamino group;each of R² and R⁵ independently represents a hydrogen atom, a halogenatom, an alkyl group, an alkenyl group, an aryl group, a heterocyclicgroup, a hydroxyl group, a cyano group, a nitro group, an alkoxy group,an aryloxy group, a heterocyclic oxy group, an acyl group, analkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, animido group, an alkoxycarbonylamino group, a sulfonamido group, an azogroup, an alkylthio group, an arylthio group, a heterocyclic thio group,an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group; eachof R³ and R⁴ independently represents a hydrogen atom, a halogen atom,an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, asilyl group, a hydroxyl group, a cyano group, an alkoxy group, anaryloxy group, a heterocyclic oxy group, an acyl group, analkoxycarbonyl group, a carbamoyl group, an anilino group, a carbonamidogroup, an ureido group, an imido group, an alkoxycarbonylamino group, asulfonamido group, an azo group, an alkylthio group, an arylthio group,a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonylgroup, a sulfamoyl group or a phosphinoylamino group; and R⁷ representsa hydrogen atom, a halogen atom, an alkyl group, an aryl group or aheterocyclic group, and

a metal atom or a metal compound selected from Zn, Mg, Si, Pt, Pd, Mo,Mn, Cu, Ni, Co, TiO or VO.

More preferred examples of the complex containing a compound representedby the formula (I) and a metal atom or a metal compound include acomplex that includes:

a compound represented by the formula (I) in which each of R¹ and R⁶independently represents a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, a cyano group, an acylgroup, an alkoxycarbonyl group, a carbamoyl group, an amino group, aheterocyclic amino group, a carbonamido group, an ureido group, an imidogroup, an alkoxycarbonylamino group, an aryloxycarbonylamino group, asulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonylgroup or a phosphinoylamino group; each of R² and R⁵ independentlyrepresents an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, a cyano group, a nitro group, an acyl group, analkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, animido group, an alkylsulfonyl group, an arylsulfonyl group or asulfamoyl group; each of R³ and R⁴ independently represents a hydrogenatom, an alkyl group, an alkenyl group, an aryl group, a heterocyclicgroup, a cyano group, an acyl group, an alkoxycarbonyl group, acarbamoyl group, a carbonamido group, an ureido group, an imido group,an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group,an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, anarylsulfonyl group or a sulfamoyl group; and R⁷ represents a hydrogenatom, a halogen atom, an alkyl group, an aryl group or a heterocyclicgroup, and

a metal atom or a metal compound selected from Zn, Mg, Si, Pt, Pd, Cu,Ni, Co or VO.

Particularly preferred examples of the complex containing a compoundrepresented by the formula (I) and a metal atom or a metal compoundinclude a complex that includes:

a compound represented by formula (I) in which each of R¹ and R⁶independently represents a hydrogen atom, an alkyl group, an aryl group,a heterocyclic group, an amino group, a heterocyclic amino group, acarbonamido group, a ureido group, an imido group, analkoxycarbonylamino group, a sulfonamido group, an azo group, analkylsulfonyl group, an arylsulfonyl group or a phosphinoylamino group;each of R² and R⁵ independently represents an alkyl group, an arylgroup, a heterocyclic group, a cyano group, an acyl group, analkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group or anarylsulfonyl group; each of R³ and R⁴ independently represents ahydrogen atom, an alkyl group, an aryl group or a heterocyclic group;and R⁷ represents a hydrogen atom, an alkyl group, an aryl group or aheterocyclic group, and

a metal atom or a metal compound selected from Zn, Cu, Co or VO.

In the formula (I), R³ and R⁴ are particularly preferably a phenyl groupin view of achieving excellent robustness. The reason for this isconsidered to be that: (1) when R³ and R⁴ are a phenyl group, thespectrum of the compound shifts to the longer wavelength side toincrease the range overlapping the spectrum of the phthalocyaninepigment that is used in combination (approximately 550 nm) that enableseasy transfer of energy; and (2) the robustness of this compound byitself is increased due to the presence of sterically bulkysubstituents.

Further, in the formula (I), R² and/or R⁵ preferably represent a2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group in view ofexcellent solubility in a solvent.

(Compound Represented by the Formula (II-1))

One of the preferable examples of the specific complex used in the firstaspect of the invention is a compound represented by the followingformula (II-1).

In the formula (II-1), each of R¹ to R⁶ independently represents ahydrogen atom or a substituent, R⁷ represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group or a heterocyclic group, Marepresents a metal atom or a metal compound, X² represents a group toneutralize a charge of Ma, and X¹ represents a group capable of beingbonded to Ma. X¹ and X² may be bonded to each other to form a 5-, 6- or7-membered ring.

It is preferred that R¹ and R⁶ are not bonded to each other to form aring.

R¹ to R⁶ in the formula (II-1) have the same definitions as that of R¹to R⁶ in the formula (I), respectively, and preferable embodimentsthereof are also the same.

Ma in the formula (II-1) represents a metal atom or a metal compoundhaving the same definitions as that of the metal atom or the metalcompound that constitutes the above-mentioned specific complex, andpreferable ranges thereof are also the same.

R⁷ in the formula (II-1) has the same definition as that of R⁷ in theformula (I), and preferable embodiments thereof are also the same.

X¹ in the formula (II-1) may be any group as long as it is capable ofbeing bonded to Ma, and examples thereof include water, alcohols (forexample, methanol, ethanol and propanol) and the like, as well as groupsderived from the compounds described in “Metal Chelates” Volume 1(1995), Volume 2 (1996) and Volume 3 (1997), authored by TakeichiSakaguchi and Kyohei Ueno and published by Nankodo, and the like. Amongthem, in view of producibility, water, carboxylic acid compounds andalcohols are preferable, and water and carboxylic acid compounds aremore preferable.

X² in the formula (II-1) represents a group to neutralize a charge ofMa, and examples thereof include a halogen atom, a hydroxyl group, acarboxylic group, a phosphoric group and a sulfonic group. Among them,in view of producibility, a halogen atom, a hydroxyl group, a carboxylicgroup and a sulfonic group are preferable, and a hydroxyl group and acarboxylic group are more preferable.

X¹ and X² in the formula (II-1) may be bonded to each other to form a5-, 6- or 7-membered ring together with Ma. The 5-, 6- or 7-memberedring may be either a saturated ring or an unsaturated ring. Further, the5-, 6- or 7-membered ring may be formed only of carbon atoms andhydrogen atoms, or may be a heterocyclic ring having at least one atomselected from a nitrogen atom, an oxygen atom or a sulfur atom.

(Compound Represented by the Formula (II-2))

One of the preferable examples of the specific complex used in the firstaspect of the invention is a compound represented by the followingformula (II-2).

In the formula (II-2), each of R¹ to R⁶ and R⁸ to R¹³ independentlyrepresents a hydrogen atom or a substituent, each of R⁷ and R¹⁴independently represents a hydrogen atom, a halogen atom, an alkylgroup, an aryl group or a heterocyclic group, and Ma represents a metalatom or a metal compound.

It is preferred that R¹ and R⁸ or R¹ and R¹³ are not bonded to eachother to form a ring, and it is preferred that R⁶ and R⁸ or R⁶ and R¹³are not bonded to each other to form a ring.

R¹ to R⁶ in the formula (II-2) have the same definitions as that of R¹to R⁶ in the formula (I), respectively, and preferable embodimentsthereof are also the same.

The substituents represented by R⁸ to R¹³ in the formula (II-2) have thesame definitions as that of the substituents represented by R¹ to R⁶ inthe compound represented by the formula (I), respectively, andpreferable embodiments thereof are also the same. When the substituentsrepresented by R⁸ to R¹³ of the compound represented by the formula(II-2) are a group that can be further substituted, the group may besubstituted by any group mentioned as Substituent R, and when the groupis substituted by two or more substituents, these substituents may bethe same or different from each other.

R⁷ in the formula (II-2) has the same definitions as that of R⁷ in theformula (I), and preferable embodiments thereof are also the same.

R¹⁴ in the formula (II-2) represents a hydrogen atom, a halogen atom, analkyl group, an aryl group or a heterocyclic group, and preferableranges of R¹⁴ are the same as the preferable ranges of R⁷. When R¹⁴represents a group that can be further substituted, the group may besubstituted by any group mentioned as Substituent R, and when the groupis substituted by two or more substituents, these substituents may bethe same or different from each other.

Ma in the formula (II-2) represents a metal atom or a metal compoundhaving the same definitions as the metal atom or the metal compound thatconstitutes the specific complex as mentioned above, and preferableranges thereof are also the same.

Combinations of R⁸ and R⁹, R⁹ and R¹⁰, R¹¹ and R¹², and R¹² and R¹³ inthe formula (II-2) may independently be bonded to each other to form a5-, 6- or 7-membered saturated or unsaturated ring. The saturated orunsaturated ring has the same definitions as that of the saturated orunsaturated ring formed by R¹ and R², R² and R³, R⁴ and R⁵, or R⁵ andR⁶, and preferable examples thereof are also the same.

(Compound Represented by the Formula (III))

One of the preferable examples of the specific complex in the firstaspect of the invention is a compound represented by the followingformula (III).

In the formula (III), each of R² to R⁵ independently represents ahydrogen atom or a substituent, R⁷ represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group or a heterocyclic group, Marepresents a metal atom or a metal compound, X³ represents NR (wherein Rrepresents a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an acyl group, an alkylsulfonyl group or anarylsulfonyl group), a nitrogen atom, an oxygen atom or a sulfur atom,X⁴ represents NRa (wherein Ra represents a hydrogen atom, an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an acylgroup, an alkylsulfonyl group or an arylsulfonyl group), an oxygen atomor a sulfur atom, Y¹ represents NRc (wherein Rc represents a hydrogenatom, an alkyl group, an alkenyl group, an aryl group, a heterocyclicgroup, an acyl group, an alkylsulfonyl group or an arylsulfonyl group),a nitrogen atom or a carbon atom, Y² represents a nitrogen atom or acarbon atom, each of R⁸ and R⁹ independently represents an alkyl group,an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group,an aryloxy group, an alkylamino group, an arylamino group or aheterocyclic amino group, R⁸ and Y¹ may be bonded to each other to forma 5-, 6- or 7-membered ring, R⁹ and Y² may be bonded to each other toform a 5-, 6- or 7-membered ring, X⁵ represents a group capable of beingbonded to Ma, and a represents 0, 1 or 2.

R² to R⁵ and R⁷ in the formula (III) have the same definitions as thatof R² to R⁵ and R⁷ in the formula (I), respectively, and preferableembodiments thereof are also the same.

Ma in the formula (III) represents a metal or a metal compound havingthe same definitions as the metal atom or the metal compound thatconstitutes the specific complex as mentioned above, and preferableranges thereof are also the same.

In the formula (III), each of R⁸ and R⁹ independently represents analkyl group (a linear, branched or cyclic alkyl group having preferably1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a t-butyl group, a hexyl group, a2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentylgroup, a cyclohexyl group or a 1-adamantyl group), an alkenyl group (analkenyl group having preferably 2 to 24 carbon atoms, more preferably 2to 12 carbon atoms, such as a vinyl group, an allyl group or a3-buten-1-yl group), an aryl group (an aryl group having preferably 6 to36 carbon atoms, more preferably 6 to 18 carbon atoms, such as a phenylgroup or a naphthyl group), a heterocyclic group (a heterocyclic grouphaving preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbonatoms, such as a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, a1-imidazolyl group, a 1-pyrazolyl group or a benzotriazol-1-yl group),an alkoxy group (an alkoxy group having preferably 1 to 36 carbon atoms,more preferably 1 to 18 carbon atoms, such as a methoxy group, an ethoxygroup, a propyloxy group, a butoxy group, a hexyloxy group, a2-ethylhexyloxy group, a dodecyloxy group or a cyclohexyloxy group), anaryloxy group (an aryloxy group having preferably 6 to 24 carbon atoms,more preferably 6 to 18 carbon atoms, such as a phenoxy group or anaphthyloxy group), an alkylamino group (an alkylamino group havingpreferably 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms,such as a methylamino group, an ethylamino group, a propylamino group, abutylamino group, a hexylamino group, a 2-ethylhexylamino group, anisopropylamino group, a t-butylamino group, a t-octylamino group, acyclohexylamino group, an N,N-diethylamino group, an N,N-dipropylaminogroup, an N,N-dibutylamino group or an N-methyl-N-ethylamino group), anarylamino group (an aryl amino group having preferably 6 to 36 carbonatoms, more preferably 6 to 18 carbon atoms, such as a phenylaminogroup, a naphthylamino group, an N,N-diphenylamino group or anN-ethyl-N-phenylamino group), or a heterocyclic amino group (aheterocyclic amino group having preferably 1 to 24 carbon atoms, morepreferably 1 to 12 carbon atoms, such as a 2-aminopyrrole group, a3-aminopyrazole group, a 2-aminopyridine group or a 3-aminopyridinegroup).

In the formula (III), when the alkyl group, alkenyl group, aryl group,heterocyclic group, alkoxy group, aryloxy group, alkylamino group,arylamino group or heterocyclic amino group represented by R⁸ or R⁹ area group that can be further substituted, the group may be substituted byany group mentioned as Substituent R, and when the group is substitutedby two or more substituents, these substituents may be the same ordifferent from each other.

In the formula (III), X³ represents NR, a nitrogen atom, an oxygen atomor a sulfur atom, X⁴ represents NRa, an oxygen atom or a sulfur atom,wherein each of R and Ra independently represents a hydrogen atom, analkyl group (a linear, branched or cyclic alkyl group having preferably1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a t-butyl group, a hexyl group, a2-ethylhexyl group, a dodecyl group, a cyclopropyl group, a cyclopentylgroup, a cyclohexyl group or a 1-adamantyl group), an alkenyl group (analkenyl group having preferably 2 to 24 carbon atoms, more preferably 2to 12 carbon atoms, such as a vinyl group, an allyl group or a3-buten-1-yl group), an aryl group (an aryl group having preferably 6 to36 carbon atoms, more preferably 6 to 18 carbon atoms, such as a phenylgroup or a naphthyl group), a heterocyclic group (a heterocyclic grouphaving preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbonatoms, such as a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, a1-imidazolyl group, a 1-pyrazolyl group or a benzotriazol-1-yl group),an acyl group (an acyl group having preferably 1 to 24 carbon atoms,more preferably 2 to 18 carbon atoms, such as an acetyl group, apivaloyl group, a 2-ethylhexyl group, a benzoyl group or a cyclohexanoylgroup), an alkylsulfonyl group (an alkylsulfonyl group having preferably1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, such as amethylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl groupor a cyclohexylsulfonyl group), or an arylsulfonyl group (anarylsulfonyl group having preferably 6 to 24 carbon atoms, morepreferably 6 to 18 carbon atoms, such as a phenylsulfonyl group or anaphthylsulfonyl group).

The alkyl group, alkenyl group, aryl group, heterocyclic group, acylgroup, alkylsulfonyl group or arylsulfonyl group represented by R or Ramay be further substituted by any group mentioned as Substituent R, andwhen the group is substituted by two or more substituents, thesesubstituents may be the same or different from each other.

In the formula (III), Y¹ represents NRc, a nitrogen atom or a carbonatom, Y² represents a nitrogen atom or a carbon atom, and Rc has thesame definitions as that of R for X³.

In the formula (III), R⁸ and Y¹ may be bonded to each other to form a5-membered ring (for example, cyclopentane, pyrrolidine,tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan,thiophene, indole, benzofuran or benzothiophene), a 6-membered ring (forexample, cyclohexane, piperidine, piperazine, morpholine,tetrahydropyran, dioxane, pentamethylenesulfide, dithiane, benzene,piperidine, piperazine, pyridazine, quinoline or quinazoline) or a7-membered ring (for example, cycloheptane or hexamethyleneimine),together with the carbon atom.

In the formula (III), R⁹ and Y² may be bonded to each other to form a5-, 6- or 7-membered ring together with the carbon atom. Examples of the5-membered, 6-membered and 7-membered rings include the rings formed byR⁸, Y¹ and the carbon atom, as mentioned above, in which one bond in thering is changed to a double bond.

In the formula (III), when the 5-, 6- or 7-membered ring formed by R⁸and Y¹ or R⁹ and Y² is a ring that can be further substituted, the ringmay be substituted by any group mentioned as Substituent R, and when thering is substituted by two or more substituents, these substituents maybe the same or different from each other.

In the formula (III), X⁵ represents a group capable of being bonded toMa, and examples thereof include the groups for X¹ in the formula(II-1); and a represents 0, 1 or 2.

Preferable embodiments of the compound represented by the formula (III)include a compound in which:

R² to R⁵, R⁷ and Ma each represent the preferable embodiments for thecomplex containing a compound represented by the formula (I) and a metalatom or a metal compound, X³ represents NR (wherein R represents ahydrogen atom or an alkyl group), a nitrogen atom or an oxygen atom, X⁴represents NRa (wherein Ra represents a hydrogen atom, an alkyl group ora heterocyclic group) or an oxygen atom, Y¹ represents NRc (wherein Rcrepresents a hydrogen atom or an alkyl group), a nitrogen atom or acarbon atom, Y² represents a nitrogen atom or a carbon atom, X⁵represents a group that is bonded via an oxygen atom, each of R⁸ and R⁹independently represents an alkyl group, an aryl group, a heterocyclicgroup, an alkoxy group or an alkylamino group, or R⁸ and Y¹ are bondedto each other to form a 5- or 6-membered ring and R⁹ and Y² are bondedto each other to form a 5- or 6-membered ring, and a represents 0 or 1.

More preferable embodiments of the compound represented by the formula(III) include a compound in which:

R² to R⁵, R⁷ and Ma each represent the preferable embodiments for thecomplex containing a compound represented by the formula (I) and a metalatom or a metal compound, X³ and X⁴ represent an oxygen atom, Y¹represents NH, Y² represents a nitrogen atom, X⁵ represents a group thatis bonded via an oxygen atom, each of R⁸ and R⁹ independently representsan alkyl group, an aryl group, a heterocyclic group, an alkoxy group oran alkylamino group, or R⁸ and Y¹ are bonded to each other to form a 5-or 6-membered ring and R⁹ and Y² are bonded to each other to form a 5-or 6-membered ring, and a represents 0 or 1.

Compound No. R¹ = R⁶ = R⁸ = R¹³ R² = R⁵ = R⁹ = R¹² R³ = R⁴ = R¹⁰ = R¹¹R⁷ = R¹⁴ Ma Ia-3  —NH₂

—CH₃ —H Zn Ia-4  same as above same as above same as above same as aboveV = 0 Ia-5  —NHCOCH₃ same as above same as above same as above Zn Ia-6 same as above same as above same as above same as above Cu Ia-7  same asabove same as above same as above —CH₃ Zn Ia-8  —NHCOCH₂OCH₂COOH same asabove same as above same as above Zn Ia-9  same as above same as abovesame as above same as above Zn Ia-10 same as above same as above—C₃H₇(iso) —H Zn Ia-11 same as above same as above same as above —CH₃ ZnIa-12 same as above same as above —C₄H₉(t) —H Cu Ia-13 —NH₂ same asabove same as above —CH₃ Zn Ia-14 same as above same as above same asabove —H Zn Ia-15 same as above same as above

same as above Zn Ia-16 —NHCOCH₃ same as above

—CH₃ Cu Ia-17 —NH₂ same as above

—H Zn Ia-18 same as above same as above same as above same as above CuIa-19 same as above same as above same as above same as above V = 0Ia-20 same as above same as above same as above —CH₃ Zn Ia-21 —NHCOCH₃same as above same as above same as above Zn Ia-22 —NHCOCH₂OCH₂COOH sameas above same as above —H Zn Ia-23 same as above same as above same asabove —CH₃ Zn

Compound No. R¹ = R⁶ = R⁸ = R¹³ R² = R⁵ = R⁹ = R¹² R³ = R⁴ = R¹⁰ = R¹¹R⁷ = R¹⁴ Ma Ia-24 —NHCOCH₂OCH₂COOH

—CH₃ Cu Ia-25 same as above same as above

same as above Zn Ia-26 same as above same as above

same as above Zn Ia-27

same as above —CH₃ —H Cu Ia-28 same as above same as above same as above—CH₃ Zn Ia-29

same as above same as above same as above Cu Ia-30 same as above same asabove

same as above Cu Ia-31

same as above

same as above Zn Ia-32

same as above same as above same as above Zn Ia-33 —NHSO₂CH₃ same asabove —CH₃ same as above Zn Ia-34

same as above same as above same as above Zn

Compound No. R¹ R² R³ R⁴ R⁹ X¹ II-1 —CH₃ —COOC₂H₅ —CH₃ —CH₃ —CH₃ H₂OII-2 same as above same as above same as above same as above

same as above II-3 same as above same as above same as above same asabove

same as above II-4

—COOCH₃ same as above

—CH₃ same as above II-5

—COOC₂H₅ same as above same as above —CH₂OCH₂COOH same as above II-6same as above same as above same as above same as above —CH₃ same asabove

Compound No. R¹ R² R³ R⁴ R⁹ X¹ II-7 —CH₃ —COOC₂H₅

—CH₃ H₂O II-8

same as above same as above same as above same as above same as aboveII-9

—CN —CH₃ —CH₃ same as above same as above  II-10

same as above same as above same as above

same as above  II-11 same as above same as above

—CH₃ same as above

Compound No. R¹ R² R³ R⁴ R⁷ R⁹ X¹ II-A —CH₃ —COOC₂H₅ —CH₃ —CH₃

—CH₃ H₂O

Compound Compound No. R⁸ R⁹ No. R⁸ R⁹ III-1 —CH₃ —CH₃ III-2

—CH₃ III-3 —C₄H₉(t) same as above III-4

III-5 —C₄H₉(t) —C₄H₉(t) III-6

—CH₃ III-7

—CH₃ III-8 —CH₂OCH₃ same as above III-9

same as above III-10

same as above III-11

same as above III-12

same as above III-13

same as above III-14

same as above III-15 —CH₂OCH₂COOC₂H₅ same as above III-16 —CH₂NHSO₂CH₃same as above III-17

same as above III-18

same as above III-19

same as above III-20

same as above III-21

same as above III-22

same as above III-23

same as above III-24

same as above

Compound No. R⁸ R⁹ Compound No. R⁸ R⁹ III-25

—CH₃ III-26 —CH₂CH₂COOC₂H₅ —CH₃ III-27

same as above III-28

same as above III-29 —CH₂NHSO₂CH₃ —CH₂NHSO₂CH₃ III-30

III-31 —CH₂NHSO₂CH₃

III-32

—C₄H₉(t) III-33

—CH₃ III-34

Compound Compound No. R⁸ R⁹ No. R⁸ R⁹ III-35

—CH₃ III-36

—CH₃ III-37

same as above III-38

same as above III-39

same as above III-40

same as above III-41

same as above III-42

same as above III-43

same as above III-44

same as above

Compound Compound No. R⁸ R⁹ No. R⁸ R⁹ III-45 —CH₃ —CH₃ III-46

III-47 —C₄H₉(t) —C₄H₉(t) III-48

III-49 —CH₂NHSO₂CH₃ —CH₃ III-50 —CH₂NHSO₂CH₃ —CH₂NHSO₂CH₃ III-51

same as above III-52

III-53

same as above III-54

—CH₃ III-55

III-56

same as above

Compound Compound No. R⁸ R⁹ No. R⁸ R⁹ III-57

—CH₃ III-58

III-59

same as above III-60

—CH₃ III-61

same as above III-62

same as above III-63

same as above III-64

III-64-2

Compound No. R³ R⁴ R⁵ R⁸ R⁹ III-65 —CH₃ —CH₃ —COOC₂H₅ —CH₃ —CH₃ III-66same as above same as above same as above

III-67 same as above same as above same as above

III-68

same as above same as above —CH₃ —CH₃ III-69

same as above same as above same as above III-70 —CH₃

same as above

Compound No. R³ R⁴ R⁵ R⁸ R⁹ III-71

—CH₃

III-72 same as above same as above

same as above same as above III-73 same as above same as above

same as above same as above III-74 same as above same as above

same as above same as above III-75 same as above same as above

same as above same as above

Compound No. R³ R⁴ R⁸ R⁹ III-76 —CH₃ —CH₃ —CH₃ —CH₃ III-77 same as abovesame as above

same as above III-78 same as above same as above same as above

III-79 same as above same as above

III-80 same as above

—CH₃ —CH₃ III-81 same as above same as above same as above

III-82 same as above same as above

same as above

Compound No. R³ R⁴ R⁸ R⁹ III-83 —CH₃

III-84 same as above same as above same as above

III-85 same as above same as above —C₄H₉(t) same as above III-86

—CH₃ —CH₃ —CH₃ III-87 same as above same as above —CH₂NHSO₂CH₃—CH₂NHSO₂CH₃ III-88

—CH₃ —CH₃ III-89 —CH₃

same as above same as above

Compound No. R³ R⁴ R⁸ R⁹ III-90 —CH₃ —CH₃ —CH₃ —CH₃ III-91 same as abovesame as above same as above

III-92 same as above same as above

same as above III-93

—CH₃ —CH₃ III-94 same as above same as above —C₄H₉(t) —C₄H₉(t) III-95same as above same as above

same as above III-96 same as above same as above

—CH₃ III-97

—CH₃ —CH₃

Compound No. R³ R⁴ R⁸ R⁹ III-98

—CH₃ —CH₃ III-99

same as above same as above III-100

same as above same as above III-101

same as above same as above III-102

III-103

Compound No. R⁷ R⁸ R⁹ III-A

—C₄H₉(t) —C₄H₉(t)

Compound No. R³ R⁴ R⁵ R⁷ R⁸ R⁹ III-B —CH₃ —CH₃ —COOC₂H₅

—CH₃ —CH₃

Compound No. R³ R⁴ R⁷ R⁸ R⁹ III-C —CH₃ —CH₃

—CH₃ —CH₃

In view of the thickness of the film, the molar absorption coefficientof the specific complex of the first aspect of the invention ispreferably as high as possible. Further, in view of improving colorpurity, the maximum absorption wavelength (λmax) is preferably in therange of from 520 nm to 580 nm, more preferably from 530 nm to 570 nm.The maximum absorption wavelength and the molar absorption coefficientcan be measured by a spectrophotometer (UV-2400PC, trade name,manufactured by Shimadzu Corporation).

In view of solubility, the melting point of the specific complex of thefirst aspect of the invention is preferably not too high.

The specific complex of the first aspect of the invention may besynthesized by the methods described in U.S. Pat. Nos. 4,774,339 and5,433,896, JP-A Nos. 2001-240761 and 2002-155052, Japanese Patent No.3614586, Aust. J. Chem, 1965, 11, 1835-1845, J. H. Boger et al,Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990), and the like.

With respect to the synthesis method of the specific complex inaccordance with the first aspect of the invention, the method describedin paragraphs [0131] to [0157] of JP-A No. 2008-292970 may bespecifically applied.

As the specific complex in accordance with the first aspect of theinvention, Complex A, in which R¹ to R⁶ in the compound represented bythe formula (I) are substituted by at least the following Substituent a(preferably Substituent a and Substituent b), is also preferred.

Substituent a: a group having an ethylenically unsaturated bond at theend thereof (more preferably, a group having an acryloyl group or amethacryloyl group at the end thereof).

Substituent b: a group having a —CO₂M group (M represents a hydrogenatom, an organic base or metal atom that is necessary for neutralizing acharge of —CO₂ ⁻, or a simple anion (that is, CO₂M represents CO₂ ⁻) atthe end thereof.

Further, Complex B, in which R² to R⁵, R⁸ and R⁹ in the compoundrepresented by the formula (III) are substituted at least by theSubstituent a (preferably, substituted by the Substituent a and theSubstituent b), is also preferred as the specific complex in accordancewith the first aspect of the invention.

The dye in accordance with the first aspect of the invention may be adye multimer obtained by polymerizing the Complex A or the Complex B.The dye multimer may also be obtained by copolymerizing the Complex A orthe Complex B with a further monomer component (for example, acrylicacid or methacrylic acid).

The Complex B is preferably a compound represented by the followingformula (2).

(Compound Represented by the Formula (2))

In the formula (2), each of R₂ to R₅ independently represents a hydrogenatom or a substituent; R₇ represents a hydrogen atom, a halogen atom, analkyl group, an aryl group or a heterocyclic group; each of R₁₀ and R₁₁independently represents an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an alkoxy group, an aryloxy group, an aminogroup, an anilino group or a heterocyclic amino group; a substituentrepresented by any of R₂ to R₅, R₁₀ or R₁₁ is a divalent linking groupbonded to -L₁- or -L₂-, or a substituent represented by any of R, to R₅,R₁₀ or R₁₁ is a single bond and -L₁- or -L₂- directly substitutes thedipyrromethene skeleton; Ma represents a metal or a metal compound; X₁represents a group to neutralize a charge of Ma; r represents 0 or 1;each of X₃ and X₄ independently represents NR(R represents a hydrogenatom, an alkyl group, an alkenyl group, an aryl, group, a heterocyclicgroup, an acyl group, an alkylsulfonyl group or an arylsulfonyl group),a nitrogen atom, an oxygen atom or a sulfur atom; each of Y₁ and Y₂independently represents NR(R represents a hydrogen atom, an alkylgroup, an alkenyl group, an aryl group, a heterocyclic group, an acylgroup, an alkylsulfonyl group or an arylsulfonyl group) or an oxygenatom; R₁₀ and Y₁ may be bonded to each other to form a five, six orseven-membered ring; R₁₁ and Y₂ may be bonded to each other to form afive, six or seven-membered ring; M represents a hydrogen atom, or anorganic base or a metal atom to neutralize a charge of —CO₂ ⁻, or ananion (i.e., CO₂M represents CO₂ ⁻); L₁ represents a single bond or a(m+1)-valent linking group; m represents 1, 2 or 3; p represents 1 or 2;R₃ represents a hydrogen atom or a methyl group; Q represents an oxygenatom or NR₉ (R₉ represents a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group or an arylsulfonyl group); L₂ represents a singlebond or an (n+1)-valent linking group; n represents 1, 2 or 3; qrepresents 1 or 2; when p is 2, the two of {(L₁)-(CO₂M)_(m)} may be thesame or different from each other; when q is 2, the two of{(L₂)-(Q-COC(R₈)═CH₂)n} may be the same or different from each other;when m is 2 or 3, the two or three of (CO₂M) may be the same ordifferent from each other; and when n is 2 or 3, the two or three of(Q-COC(R₈)═CH₂) may be the same or different from each other.

The compound represented by the formula (2) has a structure in which apolymerizable group and a carboxyl group are introduced into the samemolecule.

The compound represented by the formula (2) inhibits color transfer byhaving a polymerizable group when the compound is formed into a coloredcured film, and improves pattern formation suitability by having acarboxyl group.

Further, the compound represented by the formula (2) may also be atautomer.

In the formula (2), R₂ to R₅ have the same definitions as that of R² toR⁵ in the formula (I), respectively, and the preferable ranges thereofare also the same.

In the formula (2), R₇ has the same definitions as that of R⁷ in theformula (I), and preferable ranges thereof are also the same.

In the formula (2), each of R₁₀ and R₁₁ independently represents analkyl group, an alkenyl group, an aryl group, a heterocyclic group, analkoxy group, an aryloxy group, an amino group, an anilino group or aheterocyclic amino group.

Among them, R₁₀ and R₁₁ preferably represent an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an alkoxy group, an aryloxygroup or a heterocyclic amino group, more preferably an alkyl group, analkenyl group, an alkoxy group or an aryloxy group.

In the formula (2), any one of R₂ to R₅, R₁₀ and R₁₁ is a divalentlinking group and is bonded to -L₁- or -L₂-, or any one of R₂ to R₅, R₁₀and R₁₁ is a single bond and -L₁- or -L₂- directly substitutes thedipyrromethene backbone.

In the formula (2), the site at which -L₁- is bonded is preferably atleast one of R₃, R₄, R₁₀ and R₁₁, more preferably at least one of R₁₀and R₁₁, in view of synthesis suitability.

In the formula (2), the site at which -L₂- is bonded is preferably atleast one of R₃, R₄, R₁₀ and R₁₁, more preferably at least one of R₁₀and in view of synthesis suitability.

In the formula (2), Ma, X₁ and r have the same definitions as that ofMa, X⁵ and a in the formula (III), respectively, and the preferableranges thereof are also the same.

In the formula (2), M represents a hydrogen atom, an organic base or ametal atom that is necessary for neutralizing a charge of —CO₂ ⁻, or asimple anion (that is, CO₂M represents CO₂ ⁻).

Among them, M is more preferably a hydrogen atom or a simple anion (thatis, CO₂M represents CO₂ ⁻).

In the formula (2), L₁ represents a single bond or a (m+1)-valentlinking group.

Examples of the (m+1)-valent linking group represented by L₁ include analkyl group having 1 to 10 carbon atoms (hereinafter, in the specificexamples of the group represented by L₁, it refers to a group obtainedby removing one to m hydrogen atoms from the group, and exemplary alkylgroups include a divalent alkylene group (m=1), a trivalent alkanetriylgroup (m=2), and a tetravalent alkanetetrayl group (m=3)), an aryl grouphaving 6 to 12 carbon atoms, an alkylthioether group having 1 to 10carbon atoms, an arylthioether group having 6 to 12 carbon atoms, analkylether group having 1 to 10 carbon atoms, an arylether group having6 to 12 carbon atoms, an alkylamino group having 1 to 10 carbon atoms,an arylamino group having 6 to 12 carbon atoms, an alkylamido grouphaving 1 to 10 carbon atoms, an arylamido group having 6 to 12 carbonatoms, an alkylcarbamoyl group having 1 to 10 carbon atoms, anarylcarbamoyl group having 6 to 12 carbon atoms, an alkylsulfonamidogroup having 1 to 10 carbon atoms, an arylsulfonamido group having 6 to12 carbon atoms, an alkylsulfamoyl group having 1 to 10 carbon atoms,and an arylsulfamoyl group having 6 to 12 carbon atoms. Specificexamples of L1 include the following groups.

The (n+1)-valent linking groups represented by L₂ include an alkyl grouphaving 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms,an alkylthioether group having 1 to 10 carbon atoms, an arylthioethergroup having 6 to 12 carbon atoms, an alkylether group having 1 to 10carbon atoms, an arylether group having 6 to 12 carbon atoms, analkylamino group having 1 to 10 carbon atoms, an arylamino group having6 to 12 carbon atoms, an alkylamide group having 1 to 10 carbon atoms,an arylamide group having 6 to 12 carbon atoms, an alkylcarbamoyl grouphaving 1 to 10 carbon atoms, an arylcarbamoyl group having 6 to 12carbon atoms, an alkylsulfoneamide group having 1 to 10 carbon atoms, anarylsulfoneamide group having 6 to 12 carbon atoms, an alkylsulfamoylgroup having 1 to 10 carbon atoms, and an arylsulfamoyl group having 6to 12 carbon atoms. Specific examples of the (n+1)-valent linking groupsrepresented by L₂ include the following groups.

L₂ is more preferably selected from the following linking groups.

In the above linking groups, * represents a position to be linked to-Q-, and ** represents a position to be linked to the dipyrromethenebackbone directly or via any one of R₁ to R₆.

In the formula (2), n represents 1, 2 or 3, preferably 2 or 3, morepreferably 2.

In the formula (2), q represents 1 or 2, preferably 1.

In the formula (2), when p is 2, the two of {(L₁)-(CO₂M)_(m)} may be thesame or different from each other; when q is 2, the two of{(L₂)-(Q-COC(R₈)═CH₂)n} may be the same or different from each other;when m is 2 or 3, the two or three of (CO₂M) may be the same ordifferent from each other; and when n is 2 or 3, the two or three of(Q-COC(R₈)═CH₂) may be the same or different from each other.

In the formula (2), the group represented by -(L₁)-(CO₂M)_(m) ispreferably selected from the following groups.

In the above groups, ** represents a position to be linked to thedipyrromethene backbone directly or via any one of R₁ to R₆.

In the formula (2), the group represented by {(L₂)-(Q-COC(R₈)═CH₂)n} ispreferably selected from the following groups.

In the above groups, ** represents a position to be linked to thedipyrromethene backbone directly or via any one of R₁ to R₆.

In the formula (2), each of X₃ and X₄ independently represents NR(Rrepresents a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an acyl group, an alkylsulfonyl group or anarylsulfonyl group), a nitrogen atom, an oxygen atom or a sulfur atom.

Among them, X₃ and X₄ are preferably NR(R represents a hydrogen atom, analkyl group or an alkenyl group), a nitrogen atom, an oxygen atom or asulfur atom, more preferably NR(R represents a hydrogen atom), anitrogen atom, an oxygen atom or a sulfur atom.

In the formula (2), each of Y₁ and Y₂ independently represents NR(Rrepresents a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an acyl group, an alkylsulfonyl group or anarylsulfonyl group) or an oxygen atom.

Among them, Y₁ and Y₂ are preferably NR(R represents a hydrogen atom, analkyl group or an alkenyl group) or an oxygen atom, more preferably NR(Rrepresents a hydrogen atom) or an oxygen atom.

In the formula (2), R₁₀ and Y₁ may be bonded to each other to form afive, six or seven-membered ring, and R₁₁ and Y₂ may be bonded to eachother to form a five, six or seven-membered ring. The five, six orseven-membered ring may be the ring as previously described.

The compound represented by the formula (2) preferably has at least onesubstituent selected from the above preferred examples, more preferablymore substituents are selected from the above preferred examples, andmost preferably all of the substituents are selected from the abovepreferred examples.

The following are specific examples of the compound represented by theformula (2). However, the invention is not limited to these examples.

Among the above-mentioned exemplary compounds, in view ofdevelopability, exemplary compounds a-5 to a-8, a-13 to a-48, b-5 tob-8, b-13 to b-48, c-5 to c-8, and c-13 to c-48 are preferable, and b-5to b-8, b-13 to b-48, c-5 to c-8, c-13 to c-48, d-1, d-2, and d-3 aremore preferable.

These dye compounds can be easily synthesized according to a methoddescribed in JP-A No. 2008-292970 or the like. Further, the dyecompounds can also be synthesized by selecting starting materials withreference to the synthesis examples described in the following Examples.

Although the total concentration of the compound represented by theformula (2) in the colored curable composition varies depending on themolecular weight and the molar absorption coefficient, it is preferablyin the range of from 0.5% by mass to 80% by mass, more preferably from0.5% by mass to 70% by mass, and particularly preferably from 1% by massto 70% by mass, with respect to the total solid components of thecomposition.

The above explanation of the dye used in the first aspect of theinvention mainly relates to the specific complexes (for example,compounds represented by the formula (II-1), formula (II-2), formula(III) or formula (2)), but the dye used in the first aspect of theinvention is not limited to these specific complexes.

The content of the dye in the colored curable composition is preferablyin the range of from 5% by mass to 40% by mass, more preferably from 10%by mass to 30% by mass, and particularly preferably from 15% by mass to25% by mass, with respect to the total solid components of the coloredcurable composition, in view of adjusting color hues.

Further, the mass ratio of the phthalocyanine pigment to the dye(dye/phthalocyanine pigment) in the colored curable composition of thefirst aspect of the invention is preferably in the range of from 0.1 to5.0, more preferably from 0.5 to 3.0, and particularly preferably from0.7 to 1.5.

If the mass ratio (dye/phthalocyanine pigment) is 0.1 or more, it ispossible to more effectively adjust color hues.

If the mass ratio (dye/phthalocyanine pigment) is 5.0 or less, it ispossible to more effectively improve light fastness.

The colored curable composition of the first aspect of the invention mayuse a colorant having a different structure than that of theabove-mentioned phthalocyanine pigment, dioxazine pigment or the dye.There is no particular limitation on such a dye having a differentstructure, and any known dyes that have been conventionally used incolor filters may be used. Examples thereof include dyes described inJP-A Nos. 2002-14220, 2002-14221, 2002-14222 and 2002-14223, and U.S.Pat. Nos. 5,667,920 and 5,059,500.

Examples of the chemical structure of the dye include a pyrazole azodye, an anilino azo dye, a triphenylmethane dye, an anthraquinone dye,an anthrapyridone dye, a benzylidene dye, an oxonol dye, apyrazolotriazole azo dye, a pyridone azo dye, a cyanine dye, aphenothiazine dye, a pyrrolopyrazole azomethine dye, a xanthene dye, aphthalocyanine dye, a benzopyrane dye, and an indigo dye.

With respect to the colored curable composition of the first aspect ofthe invention, the total content of the phthalocyanine pigment, thedioxazine pigment and the dye in the total colorant components(including a pigment and a dye) is preferably in the range of from 80%by mass to 100% by mass, more preferably from 90% by mass to 100% bymass.

<Polymerizable Compound>

The colored curable composition of the first aspect of the inventioncontains a polymerizable compound.

One example of the polymerizable compound is an addition-polymerizablecompound having at least one ethylenically unsaturated double bond.Specifically, the polymerizable compound is selected from compoundshaving at least one, preferably two or more, terminal ethylenicallyunsaturated bonds. Such compounds are widely known in this industrialfield, and may be used in the first aspect of the invention withoutparticular limitation. These compounds may have any chemical form of,for example, a monomer, a prepolymer (that is, a dimer, trimer oroligomer) or a mixture thereof, or a (co)polymer thereof. Thepolymerizable compounds in the first aspect of the invention may be usedalone or in a combination of two or more thereof.

Examples of the monomer and the (co)polymer thereof include anunsaturated carboxylic acid (for example, acrylic acid, methacrylicacid, itaconic acid, crotonic acid, isocrotonic acid or maleic acid) andan ester and an amide thereof and a (co)polymer thereof, and preferableexamples include an ester of an unsaturated carboxylic acid and analiphatic polyhydric alcohol compound, an amide of an unsaturatedcarboxylic acid and an aliphatic polyvalent amine compound, and a(co)polymer thereof. Further, an adduct of an unsaturated carboxylicacid ester or amide having a nucleophilic substituent such as a hydroxylgroup, an amino group or a mercapto group with a monofunctional ormultifunctional isocyanate or epoxy, a dehydration condensate with amonofunctional or multifunctional carboxylic acid, and the like arepreferably used. Moreover, an adduct of an unsaturated carboxylic acidester or amide having an electrophilic substituent such as an isocyanategroup or an epoxy group with a monofunctional or multifunctionalalcohol, amine or thiol, and a substituted reaction product of anunsaturated carboxylic acid ester or amide having a leaving group suchas a halogen group or a tosyloxy group with a monofunctional ormultifunctional alcohol, amine or thiol are also preferable. Furtherexamples include compounds in which the unsaturated carboxylic acid isreplaced with unsaturated phosphonic acid, styrene, vinyl ether or thelike.

Compounds described in paragraphs [0095] to [0108] of JP-A No.2009-288705 are also suitably used in the first aspect of the invention.

As the polymerizable compound, the polymerizable monomer is preferably acompound having at least one addition-polymerizable ethylenicallyunsaturated group and having a boiling point of 100° C. or higher undera normal pressure. Examples thereof include monofunctional acrylates ormethacrylates such as polyethylene glycol mono(meth)acrylate,polypropylene glycol mono(meth)acrylate and phenoxyethyl (meth)acrylate;multifunctional acrylates and methacrylates such as polyethylene glycoldi(meth)acrylate, trimethylol ethane tri(meth)acrylate, neopentyl glycoldi(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate,trimethylol propane tri(acryloyloxypropyl)ether,tri(acryloyloxyethyl)isocyanurate, compounds obtained by adding ethyleneoxide or propylene oxide to a multifunctional alcohol such as glycerinor trimethylol ethane and then methacrylating the same, urethaneacrylates as described in Japanese Examined Patent Publication (JP-B)Nos. 48-41708 and 50-6034, and JP-A No. 51-37193, polyester acrylatesdescribed in JP-A No. 48-64183, JP-B Nos. 49-43191 and 52-30490, andpolyfunctional acrylates or methaycrylates, such as epoxy acrylatesobtained by reaction of an epoxy resin and (meth)acrylic acid, ormixtures thereof.

In addition, radical-polymerizable monomers represented by the followingformulae (MO-1) to (MO-5) are also suitably used. In these formulae,when T represents an oxyalkylene group, its end at the carbon atom sideis bonded to R.

In the above-mentioned formulae, n represents 0 to 14, and m represents1 to 8. Two or more of R and T existing in one molecule may be the sameor different from each other, respectively.

As the specific examples of the radical-polymerizable monomerrepresented by the formulae (MO-1) to (MO-5), the compounds described inparagraphs [0248] to [0251] of JP-A No. 2007-269779 may be suitably usedin the first aspect of the invention.

The content of the above-described polymerizable compound in the coloredcurable composition is preferably in the range of from 5% by mass to 90%by mass, more preferably from 10% by mass to 80% by mass, andparticularly preferably from 15% by mass to 50% by mass, with respect tothe solid content of the composition. If the content of thepolymerizable compound is within the above-specified range, sufficientcurability and dissolvability of unexposed portions may be retained, andsufficient curability of exposed portions may be maintained, wherebysignificant reduction in dissolvability of unexposed portions may beprevented.

<Polymerization Initiator>

The colored curable composition of the first aspect of the inventionincludes a polymerization initiator.

The polymerization initiator is not particularly limited as long as itcan cause polymerization of a polymerizable compound as mentioned above,and is preferably selected in view of physical properties, initiationefficiency, absorption wavelength, availability, costs and the like.

The polymerization initiator is preferably a photopolymerizationinitiator. Examples of the photopolymerization initiator include atleast one active halogen compound selected from halomethyloxadiazolecompounds and halomethyl-s-triazine compounds, a 3-aryl-substitutedcoumarin compound, a lophine dimer, a benzophenone compound, anacetophenone compound and a derivative thereof, acyclopentadiene-benzene-iron complex and a salt thereof, and an oximecompound. Specific examples of the photopolymerization initiator includethose described in the paragraphs [0070] to [0077] of JP-A No.2004-295116.

Among these, an oxime compound (hereinafter, also referred to as an“oxime photopolymerization initiator”) is preferable in view of causingrapid polymerization reaction or the like.

The oxime photopolymerization initiator is not particularly limited, andexamples thereof include the oxime compounds described in, for example,JP-A No. 2000-80068 (paragraphs [0004] to [0296]), WO02/100903A1, JP-ANo. 2001-233842, JP-A No. 2006-342166 (paragraphs [0004] to [0264]), andthe like.

Specific examples of the oxime photopolymerization initiator include,but are not limited to,2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-butanedione,

-   2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-pentanedione,-   2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-hexanedione,-   2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-heptanedione,-   2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione,-   2-(O-benzoyloxime)-1-[4-(methylphenylthio)phenyl]-1,2-butanedione,-   2-(O-benzoyloxime)-1-[4-(ethylphenylthio)phenyl]-1,2-butanedione,-   2-(O-benzoyloxime)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione,-   1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,-   1-(O-acetyloxime)-1-[9-methyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,-   1-(O-acetyloxime)-1-[9-propyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,-   1-(O-acetyloxime)-1-[9-ethyl-6-(2-ethylbenzoyl)9H-carbazol-3-yl]ethanone,    and-   1-(O-acetyloxime)-1-[9-ethyl-6-(2-butylbenzoyl)-9H-carbazol-3-yl]ethanone.

Among them, oxime-O-acyl compounds, such as2-(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione and1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone,are particularly preferable in view of obtaining a pattern having afavorable shape (in particular, favorable rectangularity of a patternfor solid-state image sensors) with a smaller exposure dose, andspecific examples thereof include CGI-124 and CGI-242 (all trade names,manufactured by BASF Japan).

Further, as the polymerization initiator, an oxime photopolymerizationinitiator represented by the following formula (OX-1), as described inJP-A No. 2007-269779 (paragraphs [0016] to [0082]), is also preferable.

In the formula (OX-1), R^(1′) represents a substituent including anaromatic ring or a heteroaromatic ring. R^(1a) represents an alkyl grouphaving at least one substituent selected from the following Group (A).R^(2a) represents an alkanoyl group, an alkenoyl group, an aryloylgroup, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclicoxycarbonyl group, a heteroaryloxycarbonyl group, an alkylthiocarbonylgroup, an arylthiocarbonyl group, a heterocyclic thiocarbonyl group, aheteroarylthiocarbonyl group, —CO—CO-Rd (Rd represents an aromatic ringor heteroaromatic ring that may have a substituent). n represents aninteger of 1 to 6.

<Group (A)> a cyano group, an alkenyl group, an alkynyl group, —NArAr′,—SAr, —COOH, —CONRaRb, —NRa—CO—Rb, —O—CO—NRaRb, —NRa—CO—ORb,—NRa—CO—NRaRb, —SO-Rc, —SO₂—Rc, —O—SO₂—Rc, —SO₂—NRaRb, —NRa—SO₂—Ra,—CO—NRa—CORb, —CO—NRa—SO₂—Rb, —SO₂—NRa—CO—Rb, —SO₂—NRa—SO₂—Rc,—Si(Ra)_(l)(ORb)_(m), and a heterocyclic group. Each of Ar and Ar′independently represents an aromatic ring or heteroaromatic ring thatmay have a substituent, each of Ra and Rb independently represents ahydrogen atom or an alkyl group, aromatic ring or heteroaromatic ring,which may have a substituent, Rc represents an alkyl group, an aromaticring or a heteroaromatic ring, which may have a substituent, and each ofl and m independently represents an integer of 0 to 3, which satisfyl+m=3.

In the first aspect of the invention, in view of sensitivity, stabilityover time and coloring during post-heating, a compound represented bythe following formula (OX-2) is more preferable as the oxime compound.

In the formula (OX-2), each of R and X independently represents amonovalent substituent, A represents a divalent organic group, Arrepresents an aryl group, and n represents an integer of 1 to 5.

From the viewpoint of increasing sensitivity, R is preferably an acylgroup and preferable specific examples thereof include an acetyl group,a propionyl group, a benzoyl group and a toluoyl group.

From the viewpoint of increasing sensitivity and suppressing colorationdue to heating over time, A is preferably an unsubstituted alkylenegroup, an alkylene group substituted by an alkyl group (for example, amethyl group, an ethyl group, a tert-butyl group or a dodecyl group), analkylene group substituted by an alkenyl group (for example, a vinylgroup or an allyl group), or an alkylene group substituted by an arylgroup (for example, a phenyl group, a p-tolyl group, a xylyl group, acumenyl group, a naphthyl group, an anthryl group, a phenanthryl groupor a styryl group).

From the viewpoint of increasing sensitivity and suppressing colorationdue to heating over time, Ar is preferably a substituted orunsubstituted phenyl group. When the phenyl group is substituted, thesubstituent is preferably a halogen group such as a fluorine atom, achlorine atom, a bromine atom or an iodine atom.

From the viewpoint of improving solubility in a solvent and absorptionefficiency at a longer wavelength range, X is preferably an alkyl groupthat may be substituted, an aryl group that may be substituted, analkenyl group that may be substituted, an alkynyl group that may besubstituted, an alkoxy group that may be substituted, an aryloxy groupthat may be substituted, an alkylthioxy group that may be substituted,an arylthioxy group that may be substituted, or an amino group that maybe substituted.

In the formula (OX-2), n preferably represents an integer of 1 to 2.

The following are specific examples of the compound represented by theformula (OX-2), but the invention is not limited thereto.

Besides the above-mentioned photopolymerization initiators, other knownphotopolymerization initiators described in the paragraph [0079] of JP-ANo. 2004-295116 may be used for the colored curable composition of thefirst aspect of the invention.

The photopolymerization initiator may be used alone or in a combinationof two or more kinds.

The content of the photopolymerization initiator (when two or more kindsof photopolymerization initiators are used, the total content thereof)in the total solid content of the colored curable composition ispreferably in the range of from 3% by mass to 20% by mass, morepreferably from 4% by mass to 19% by mass, and particularly preferablyfrom 5% by mass to 18% by mass, in view of more effectively achievingthe effect of the first aspect of the invention.

<Solvent>

The colored curable composition of the first aspect of the inventionincludes a solvent.

The solvent is not particularly limited as long as it can satisfy thesolubility of the coexisting components or the coatability of thecolored curable composition, and is preferably selected particularly inview of solubility of a binder with respect to the solvent, coatabilityand safety.

Examples of the solvent include esters including ethyl acetate, n-butylacetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutylacetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butylbutyrate, methyl lactate, ethyl lactate, alkyl oxyacetates (for example,methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate (specifically,methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate,methyl ethoxyacetate and ethyl ethoxyacetate)), alkyl 3-oxypropionates(for example, methyl 3-oxypropionate and ethyl 3-oxypropionate(specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate,methyl 3-ethoxypropionate and ethyl 3-ethoxypropionate)), and alkyl2-oxypropionates (for example, methyl 2-oxypropionate, ethyl2-oxypropionate and propyl 2-oxypropionate (specifically, methyl2-methoxypropionate, ethyl 2-methoxypropionate, propyl2-methoxypropionate, methyl 2-ethoxypropionate and ethyl2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl2-oxy-2-methylpropionate (specifically, methyl2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate)),methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate,ethyl acetoacetate, methyl 2-oxobutanoate, and ethyl 2-oxobutanate.

Examples of the ethers include diethylene glycol dimethyl ether,tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate,diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,diethylene glycol monobutyl ether, propylene glycol monomethyl ether,propylene glycol monomethyl ether acetate, propylene glycol monoethylether acetate and propylene glycol monopropyl ether acetate.

Examples of the ketones include methyl ethyl ketone, cyclohexanone,2-heptanone and 3-heptanone.

Preferable examples of the aromatic hydrocarbons include toluene andxylene.

It is also preferable to mix two or more kinds of solvents in view ofthe solubility of each component, the solubility of an alkali-solublebinder when it is included, and the coating surface properties. When amixed solution of the solvent is used, it is particularly preferably amixture of at least two solvents selected from methyl3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate,ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate,butyl carbitol acetate, propylene glycol methyl ether, and propyleneglycol methyl ether acetate.

The solvent is preferably used in the colored curable composition in anamount that makes the total solid component concentration to be from 10%by mass to 80% by mass, more preferably from 15% by mass to 60% by mass.

<Dispersant>

The colored curable composition of the first aspect of the inventionpreferably contains a dispersant.

As the dispersant, a known pigment dispersant or surfactant may be used.

Many kinds of compounds may be used as the dispersant, and examplesthereof include cationic surfactants such as a phthalocyanine derivative(commercial product, trade name: EFKA-745 (manufactured by Efka),SOLSPERSE 5000 (trade name, manufactured by Lubrizol Japan Ltd.); anorganosiloxane polymer KP341 (trade name, manufactured by Shin-EtsuChemical Co., Ltd.), (meth)acrylic acid (co)polymers POLYFLOW Nos. 75,90 and 95 (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.)and W001 (trade name, manufactured by Yusho Co., Ltd.); nonionicsurfactants such as polyoxyethylene lauryl ether, polyoxyethylenestearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenylether, polyoxyethylene nonyl phenyl ether, polyethylene glycoldilaurate, polyethylene glycol distearate and sorbitan fatty acidesters; anionic surfactants such as W004, W005 and W017 (all tradenames, manufactured by Yusho Co., Ltd.); polymer dispersants such asEFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKAPOLYMER 401 and EFKA POLYMER 450 (all trade names, manufactured byMorishita & Co., Ltd.) and DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID15 and DISPERSE AID 9100 (all trade names, manufactured by San NopcoLtd.); SOLSPERSE dispersants such as SOLSPERSE 3000, 5000, 9000, 12000,13240, 13940, 17000, 24000, 26000 and 28000 (all trade names,manufactured by Lubrizol Japan Ltd.); ADEKA PLURONIC L31, F38, L42, L44,L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 andP-123 (all trade names, manufactured by Adeka Corporation), and ISONETS-20 (trade name, manufactured by Sanyo Chemical Industries, Ltd.)

When the colored curable composition of the first aspect of theinvention includes a dispersant, the content of the dispersant in thecolored curable composition is preferably from 1% by mass to 80% bymass, more preferably from 5% by mass to 70% by mass, and mostpreferably from 10% by mass to 60% by mass, with respect to the pigment.

<Pigment Derivative>

The colored curable composition of the first aspect of the invention maycontain a pigment derivative.

The pigment derivative present in the first aspect of the invention is acompound in which an acidic group, a basic group or an aromatic group asa substituent is introduced into a side chain of an organic pigment.

In the first aspect of the invention, by allowing a pigment derivativehaving a moiety having affinity with the dispersant to be adsorbed to asurface of the pigment, and using the same as an adsorption point of thedispersant, the pigment can be dispersed in the colored composition asfine particles, and reaggregation thereof can be prevented. In otherwords, the pigment derivative has an effect of accelerating theadsorption of the dispersant by modifying the pigment surface.

When the dispersant has an acidic group, dispersibility of the pigmentcan be further improved and fine particles of the pigment can be moreeffectively dispersed by using a basic pigment derivative having a basicgroup as a pigment derivative. Further, by using a colored compositionincluding a basic pigment derivative, a color filter that exhibitssuppressed color density uneveness and favorable color properties can beformed.

The pigment derivative used in the first aspect of the invention is,specifically, a compound having an organic pigment as a mother skeleton,and a substituent such as an acidic group, a basic group or an aromaticgroup being introduced to a side chain of the mother skeleton. Specificexamples of the organic pigment to serve as a mother skeleton include aquinacridone pigment, a phthalocyanine pigment, an azo pigment, aquinophthalone pigment, an isoindoline pigment, an isoindolinonepigment, a quinoline pigment, a diketopyrrolopyrrole pigment, and abenzimidazolone pigment. Pale yellow aromatic polycyclic compounds suchas a naphthalene compound, an anthraquinone compound, a triazinecompound and a quinoline compound, which are typically not included indyes, are also usable as a mother skeleton.

Further, examples of the pigment derivative in the first aspect of theinvention also include those described in JP-A Nos. 11-49974, 11-189732,10-245501, 2006-265528, 8-295810, 11-199796, 2005-234478, 2003-240938,2001-356210, and the like.

When a pigment derivative is used in the colored composition of thefirst aspect of the invention, the amount of the pigment derivative tobe used is preferably in the range of from 1% by mass to 80% by mass,more preferably from 3% by mass to 65% by mass, yet more preferably from5% by mass to 50% by mass, with respect to the mass of the pigment. Whenthe content of the pigment derivative is within the above-specifiedrange, the pigment can be favorable dispersed while suppressing theviscosity at a low level, whereby dispersion stability after thedispersion can be improved. In addition, by using the thus obtainedcolored composition, color filters that exhibit high transmissivity,excellent color properties and high contrast can be obtained.

<Other Components>

The colored curable composition of the first aspect of the invention mayfurther contain other components such as a resin or a crosslinkingagent, in addition to the above-mentioned components, to such an extentthat the effect of the invention is not deteriorated.

—Resin—

As a resin to be used in the colored curable composition, analkali-soluble binder is suitably used.

The alkali-soluble binder is not particularly limited as long as it hasalkali solubility, and may be preferably selected in view of heatresistance, developability, availability and the like.

Preferable examples of the alkali-soluble binder include a linearorganic high molecular weight polymer that is soluble in an organicsolvent and is developable with a weak alkali aqueous solution. Examplesof such linear organic high molecular weight polymers include polymershaving carboxylic acid in a side chain, such as methacrylic acidcopolymers, acrylic acid copolymers, itaconic acid copolymers, crotonicacid copolymers, maleic acid copolymers and partially-esterified maleicacid copolymers as described in JP-A No. 59-44615, JP-B Nos. 54-34327,58-12577 and 54-25957 and JP-A Nos. 59-53836 and 59-71048. Acidiccellulose derivatives having carboxylic acids in side chains are alsouseful.

In addition to the above-mentioned binders, adducts of polymers havinghydroxyl groups with acid anhydrides, polyhydroxystyrene resins,polysiloxane resins, poly(2-hydroxyethyl(meth)acrylate), polyvinylpyrrolidone, polyethylene oxides, polyvinyl alcohols, and the like arealso useful as the alkali-soluble binder in the first aspect of theinvention. The linear organic high molecular weight polymer may be acopolymerization product of a hydrophilic monomer. Examples thereofinclude alkoxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates,glycerol (meth)acrylates, (meth)acrylamides, N-methylolacrylamides,secondary or tertiary alkylacrylamides, dialkylaminoalkyl(meth)acrylates, morpholine (meth)acrylates, N-vinylpyrrolidone,N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl(meth)acrylates, ethyl (meth)acrylates, branched or linear propyl(meth)acrylates, branched or linear butyl (meth)acrylates, andphenoxyhydroxy propyl(meth)acrylates. Other examples of the hydrophilicmonomer include monomers containing a tetrahydrofurfuryl group, aphosphoric acid group, a phosphoric acid ester group, a quaternaryammonium salt group, an ethyleneoxy chain, a propyleneoxy chain, asulfonic acid group or a group derived from a salt thereof, or amorpholinoethyl group.

The alkali-soluble binder may have a polymerizable group in a side chainthereof in order to improve crosslinking efficiency. For example,polymers having an allyl group, a (meth)acryl group, an allyloxyalkylgroups or the like in a side chain thereof, and the like are alsouseful. Examples of the polymer having a polymerizable group includecommercial products such as KS RESIST-106 (trade name, manufactured byOsaka Organic Chemical Industry Ltd.) and CYCLOMER-P series (all tradenames, manufactured by Daicel Chemical Industries, Ltd.) Further, inorder to improve the strength of a cured film, an alcohol-soluble nylonand a polyether of 2,2-bis-(4-hydroxyphenyl)propane and epichlorohydrinare also useful.

The alkali-soluble binder to be used is preferably a polymer (a), whichobtained by polymerizing a compound represented by the following formula(E-1) (hereinafter, also referred to as an “ether dimer”).

In the formula (E-1), each of R¹ and R² independently represents ahydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms whichmay have a substituent.

When the colored curable composition of the first aspect of theinvention contains the polymer (a), heat resistance and transparency ofa cured film formed from the composition can be further improved.

In the formula (E-1) representing an ether dimer, the hydrocarbon grouphaving 1 to 25 carbon atoms which may have a substituent, represented byR¹ and R², is not particularly limited, and examples thereof include alinear or branched alkyl group such as a methyl group, an ethyl group,an n-propyl group, an isopropyl group, an n-butyl group, an isobutylgroup, a t-butyl group, a t-amyl group, a stearyl group, a lauryl groupor a 2-ethylhexyl group; an aryl group such as a phenyl group; acycloaliphatic group such as a cyclohexyl group, a t-butyl cyclohexylgroup, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornylgroup, an adamantyl group or a 2-methyl-2-adamantyl group; analkoxy-substituted alkyl group such as a 1-methoxyethyl group or a1-ethoxyethyl group; and an aryl group-substituted alkyl group such as abenzyl group.

Among them, a group including a primary or secondary carbon, such as amethyl group, an ethyl group, a cyclohexyl group or a benzyl group thatis less likely to detach due to acid or heat, is preferable in view ofheat resistance.

The substituents represented by R¹ and R² may be the same or differentfrom each other.

Specific examples of the ether dimer include:

-   dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate,-   diethyl-2,2′-[oxybis(methylene)]bis-2-propenoate,-   di(n-propyl)-2,2′[oxybis(methylene)]bis-2-propenoate,-   di(isopropyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,-   di(n-butyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,-   di(isobutyl)-2,2′[oxybis(methylene)]bis-2-propenoate,-   di(t-butyl)-2,2′[oxybis(methylene)]bis-2-propenoate,-   di(t-amyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,-   di(stearyl)-2,2′[oxybis(methylene)]bis-2-propenoate,-   di(lauryl)-2,2′-[oxybis(methylene)]bis-2-propenoate,-   di(2-ethylhexyl)-2,2′[oxybis(methylene)]bis-2-propenoate,-   di(1-methoxyethyl)-2,2′4-[oxybis(methylene)]bis-2-propenoate,-   di(1-ethoxyethyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,-   dibenzyl-2,2′-[oxybis(methylene)]bis-2-propenoate,-   diphenyl-2,2′1-[oxybis(methylene)]bis-2-propenoate,-   dicyclohexyl-2,2′4-[oxybis(methylene)]bis-2-propenoate,-   di(t-butylcyclohexyl)-2,2′4-[oxybis(methylene)]bis-2-propenoate,-   di(dicyclopentadienyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,-   di(tricyclodecanyl)-2,2′1-[oxybis(methylene)]bis-2-propenoate,-   di(isobornyl)-2,2′-[oxybis(methylene)]bis-2-propenoate,-   diadamantyl-2,2′-[oxybis(methylene)]bis-2-propenoate, and-   di(2-methyl-2-adamantyl)-2,2′4-[oxybis(methylene)]bis-2-propenoate.

Among them, dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate,diethyl-2,2′-[oxybis(methylene)]bis-2-propenoate,dicyclohexyl-2,2′-[oxybis(methylene)]bis-2-propenoate, anddibenzyl-2,2′[oxybis(methylene)]bis-2-propenoate are preferable. Theseether dimers may be used alone or in a combination of two or more kindsthereof.

A polymer having an epoxy group is also suitable as the alkali-solublebinder.

An epoxy group can be introduced into the alkali-soluble binder by, forexample, using a monomer having an epoxy group (hereinafter, alsoreferred to as a “monomer for introducing an epoxy group”) forpolymerization as a monomer component. Examples of such monomers havingan epoxy group include glycidyl (meth)acrylate,3,4-epoxycyclohexylmethyl (meth)acrylate and o-, m- orp-vinylbenzylglycidyl ether. These monomers for introducing an epoxygroup may be used alone or in a combination of two or more kindsthereof. When the monomer components used for obtaining analkali-soluble binder include a monomer for introducing an epoxy group,the content thereof is not particularly limited but preferably in therange of from 5% by mass to 70% by mass, more preferably from 10% bymass to 60% by mass, with respect to the total mass of the monomercomponents.

A polymer having an acidic group is also suitable as the alkali-solublebinder.

The acidic group is not particularly limited, and examples thereofinclude a carboxy group, a phenolic hydroxyl group, and a carboxylicacid anhydride group. These acidic groups may be used alone or in acombination of two or more kinds thereof. In order to introduce anacidic group into the alkali-soluble binder, for example, a monomerhaving an acidic group and/or a monomer capable of imparting an acidicgroup after polymerization (hereinafter, also referred to as a “monomerfor introducing an acid group”) may be used for polymerization as amonomer component.

When an acidic group is introduced by means of the monomer capable ofimparting an acidic group after polymerization as a monomer component,for example, a treatment for imparting an acidic group, such asdescribed hereinafter, needs to be carried out after the polymerization.

Examples of the monomer having an acidic group include a monomer havinga carboxy group, such as (meth)acrylic acid or itaconic acid; a monomerhaving a phenolic hydroxyl group, such as N-hydroxyphenylmaleimide; anda monomer having a carboxylic acid anhydride group, such as maleicanhydride or itaconic anhydride. Particularly among them, (meth)acrylicacid is preferable.

Examples of the monomer capable of imparting an acid group afterpolymerization include a monomer having a hydroxyl group, such as2-hydroxyethyl (meth)acrylate; a monomer having an epoxy group such asglycidyl (meth)acrylate; and a monomer having an isocyanate group, suchas 2-isocyanatoethyl(meth)acrylate. These monomers for introducing anacidic group may be used alone or in a combination of two or morethereof.

When the monomer capable of imparting an acidic group afterpolymerization is used, examples of the treatment for imparting anacidic group after polymerization include a treatment of partiallymodifying polar groups of the polymer side chain through polymerreaction.

Among these alkali-soluble binders, a polyhydroxystyrene resin, apolysiloxane resin, an acrylic resin, an acrylamide resin and anacryl/acrylamide copolymer resin are preferable in view of heatresistance, and an acrylic resin, an acrylamide resin and anacryl/acrylamide copolymer resin are preferable in view of controllingthe developability.

Preferred examples of the acrylic resins include copolymers formed froma monomer selected from benzyl (meth)acrylate, (meth)acrylic acid,hydroxyethyl (meth)acrylate, (meth)acrylamide or the like, andcommercial products such as KS RESIST-106 (trade name, manufactured byOsaka Organic Chemical Industry Ltd.) and CYCLOMER-P series (all tradenames, manufactured by Daicel Chemical Industries, Ltd.)

The alkali-soluble binder is a polymer having a weight average molecularweight (polystyrene-converted value measured by GPC) of preferably from1,000 to 2×10⁵, more preferably from 2,000 to 1×10⁵, and particularlypreferably from 5,000 to 5×10⁴, in view of developability, liquidviscosity or the like.

The acid value of the alkali-soluble binder is preferably in the rangeof from 50 mgKOH/g to 300 mgKOH/g, more preferably from 75 mgKOH/g to200 mgKOH/g, and particularly preferably from 80 mgKOH/g to 160 mgKOH/g.When the acid value of the alkali-soluble binder is within theabove-specified range, remaining of development residues during theformation of a pattern can be suppressed, and coating uniformity can beimproved.

—Crosslinking Agent—

A crosslinking agent may be used as a supplemental agent in the coloredcurable composition of the first aspect of the invention, in order tofurther increase the hardness of the colored cured film formed from thecolored curable composition.

The crosslinking agent is not particularly limited as long as it cancure a film by crosslinking reaction, and examples thereof include (a)an epoxy resin, (b) a melamine compound, a guanamine compound, aglycoluril compound or an urea compound substituted by at least oneselected from a methylol group, an alkoxymethyl group or anacyloxymethyl group, and (c) a phenol compound, a naphthol compound or ahydroxyanthracene compound substituted by at least one selected from amethylol group, an alkoxymethyl group or an acyloxymethyl group. Amongthese, multifunctional epoxy resins are preferable.

Details of the specific examples and the like of the crosslinking agentcan be found in the paragraphs [0134] to [0147] of JP-A No. 2004-295116.

—Polymerization Inhibitor—

In the colored curable composition of the first aspect of the invention,it is preferred to add a small amount of a polymerization inhibitor inorder to prevent unnecessary thermal polymerization of the polymerizablecompound during the production or storage.

Examples of the polymerization inhibitor useful in the first aspect ofthe invention include hydroquinone, p-methoxyphenol,di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone,4,4′-thiobis(3-methyl-6-t-butylphenol),2,2′-methylenebis(4-methyl-6-t-butylphenol), andN-nitrosophenylhydroxyamine primary cerium salt.

The addition amount of the polymerization inhibitor is preferably in therange of about 0.01% by mass to about 5% by mass with respect to thetotal mass of the composition.

—Surfactant—

The colored curable composition of the first aspect of the invention maycontain a surfactant in view of further improving the coatability.Examples of the surfactants that may be used in the prevent inventioninclude various surfactants such as a fluorosurfactant, a nonionicsurfactant, a cationic surfactant, an anionic surfactant, and a siliconesurfactant.

In particular, by using a fluorosurfactant, liquid properties (inparticular, fluidity) of the composition as a coating liquid can befurther improved, thereby further improving the uniformity of thecoating thickness and saving the amount of liquid to be used.

Specifically, when a colored curable composition containing afluorosurfactant is used, the surface tension between a surface of thesubstrate to be coated and the coating liquid is decreased and thewettability to the surface to be coated is improved, thereby improvingthe coatability. As a result, a film having a uniform thickness withsuppressed unevenness can be favorably formed even when a film having athickness of as small as several micrometers is formed with a smallliquid amount.

The fluorine content in the fluorosurfactant is preferably in the rangeof from 3% by mass to 40% by mass, more preferably from 5% by mass to30% by mass, and particularly preferably from 7% by mass to 25% by mass.When the fluorine content is within the above-specified range, it iseffective to achieve the uniformity in the coating film thickness andsave the amount of liquid to be used, while the solubility in thecomposition is favorable.

Examples of the fluorosurfactant include MEGAFAC F171, F172, F173, F176,F177, F141, F142, F143, F144, R30, F437, F479, F482, F780 and F781 (alltrade names, manufactured by DIC Corporation), FLUORAD FC430, FC431 andFC171 (all trade names, manufactured by Sumitomo 3M Limited), SURFLONS-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, 5393 andKH-40 (all trade names, manufactured by Asahi Glass Co., Ltd.), and CW-1(trade name, manufactured by Zeneca).

Specific examples of the cationic surfactant include a phthalocyaninederivative (commercial product, trade name: EFKA-745, manufactured byMorishita & Co., Ltd.), an organosiloxane polymer (trade name: KP341,manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid(co)polymers POLYFLOW No. 75, No. 90 and No. 95 (all trade names,manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (trade name,manufactured by Yusho Co., Ltd.).

Specific examples of the nonionic surfactant include polyoxyethylenelauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleylether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenylether, polyethylene glycol dilaurate, polyethylene glycol distearate,and sorbitan fatty acid ester (such as PLURONIC L10, L31, L61, L62,10R5, 17R2 and 25R2, and TETRONIC 304, 701, 704, 901, 904 and 150R1, alltrade names, manufactured by BASF).

Specific examples of the anionic surfactant include W004, W005 and W017(all trade names, manufactured by Yusho Co., Ltd.).

Examples of the silicone surfactant include “TORAY SILICONE DC3PA”,“TORAY SILICONE SH7PA”, “TORAY SILICONE DC11PA”, “TORAY SILICONESH21PA”, “TORAY SILICONE SH28PA”, “TORAY SILICONE SH29PA”, “TORAYSILICONE SH30PA” and “TORAY SILICONE SH8400” (all trade names,manufactured by Toray Silicone Co., Ltd.), “TSF-4440”, “TSF-4300”,“TSF-4445”, “TSF-444(4)(5)(6)(7)6”, “TSF-44 60” and “TSF-4452” (alltrade names, manufactured by Toshiba Silicone Co., Ltd.), “KP341” (tradename, manufactured by Silicone Co., Ltd.), and “BYK323” and “BYK330”(all trade names, manufactured by BYK Chemie).

These surfactants may be used in a combination of two or more kindsthereof.

—Organic Carboxylic Acid—

Further, in view of enhancing the alkali solubility of non-exposedportions and further improving the developability of the colored curablecomposition, an organic carboxylic acid, preferably alow-molecular-weight organic carboxylic acid having a molecular weightof 1,000 or less, is preferably added to the composition.

Specific examples of the organic carboxylic acid include aliphaticmonocarboxylic acids such as formic acid, acetic acid, propionic acid,butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetate,enanthic acid and caprylic acid; aliphatic dicarboxylic acids such asoxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid,methyl malonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid and citraconic acid; aliphatictricarboxylic acids such as tricarballylic acid, aconitic acid andcamphoronic acid; aromatic monocarboxylic acids such as benzoic acid,toluic acid, cuminic acid, hemellitic acid and mesitylenic acid;aromatic polycarboxylic acids such as phthalic acid, isophthalic acid,terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid andpyromellitic acid; and other carboxylic acids such as phenyl aceticacid, hydratropic acid, hydrocinnamic acid, mandelic acid,phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate,benzyl cinnamate, cinnamylidene acetic acid, coumaric acid and umbellicacid.

—Other Additives—

Various additives including fillers, polymer compounds other than thosementioned above, adhesion accelerating agents, antioxidants, ultravioletabsorbers, and aggregation inhibitors may be optionally incorporatedinto the colored curable composition. These additives include thosedescribed in the paragraphs [0155] to [0156] of JP-A No. 2004-295116.

Further, the colored curable composition of the first aspect of theinvention may contain the sensitizer and light stabilizer described inthe paragraph [0078] of JP-A No. 2004-295116 and the thermalpolymerization inhibitor described in the paragraph [0081] of the samepublication.

<Preparation Method of Colored Heat-Curable Composition>

The colored heat-curable composition of the first aspect of theinvention is prepared by mixing the above-mentioned essentialcomponents, and optional components as necessary.

During the preparation of the colored curable composition, thecomponents that constitute the colored curable composition may be mixedat one time, or may be mixed after dissolving or dispersing eachcomponent in a solvent, respectively. The order of addition duringmixing or the operation conditions are not particularly limited. Forexample, the composition may be prepared by simultaneously dissolving ordispersing all components in a solvent, or alternatively, thecomposition may be prepared from previously prepared two or moresolutions or dispersions each containing part of the components at thetime of using (applying) the composition.

The thus prepared colored curable composition may be subjected tofilteration prior to using the same, with a Millipore filter or the likehaving a pore diameter of preferably from about 0.01 μm to 3.0 μm, morepreferably from about 0.05 μm to 0.5 μm.

Since the colored curable composition of the first aspect of theinvention exhibits excellent storage stability and can form a coloredcured film having excellent light fastness, the composition can besuitably used for forming color pixels of color filters used for liquidcrystal display devices (LCDs) or solid-state image sensors (forexample, CCD and CMOS image sensors). Further, the composition can besuitably used for preparing printing inks, inkjet inks, paints or thelike. The composition is particularly suitably used for forming colorpixels (color filters) for solid-state image sensors such as CCD andCMOS image sensors.

<Color Filter and Production Method Thereof>

In the following, a method for producing a color filter using thecolored curable composition of the first aspect of the invention (methodfor producing the color filter of the first aspect of the invention)will be described.

The method for producing the color filter of the first aspect of theinvention includes (A) a step of applying the colored curablecomposition of the first aspect of the invention onto a support to forma colored curable composition layer, and (B) a step of exposing thecolored curable composition layer formed in the step (A) through a mask,and developing the exposed colored curable composition layer to form acolored pattern.

The method for producing the color filter of the first aspect of theinvention preferably further includes (C) a step of irradiating thecolored pattern formed in the step (B), with ultraviolet radiation, and(D) a step of heat-treating the colored pattern that has been irradiatedwith ultraviolet radiation in the step (C).

Hereinafter, the method for producing the color filter of the firstaspect of the invention will be described more specifically.

—Step (A)—

In the method for producing the color filter of the first aspect of theinvention, the colored curable composition of the first aspect of theinvention is applied onto a support by a coating process such as spincoating, casting coating or roll coating, to form a colored curablecomposition layer, and optionally subjecting the colored curablecomposition layer to preliminary curing (pre-baking) for drying thesame.

Examples of the support used for the production method of the colorfilter of the first aspect of the invention include soda glass,borosilicate glass (trade name: PYREX®) and quartz glass, which are usedfor LCDs or the like, and these glass supports on which a transparentelectroconductive film has been attached, photoelectric conversiondevice substrates used for imaging devices, such as silicon substrates,and complementary metal oxide film semiconductor (CMOS) substrates.Black stripes that isolate the pixels from each other may be formed onthe support. Further, a primer layer may be formed on these supports forthe purpose of improving the adhesion to an upper layer, preventingdiffusion of the materials, or smoothing the surface of the support.

When the colored curable composition is spin-coated on the support, inorder to reduce the amount of the composition to be dropped on thesupport, a suitable organic solvent may be dropped on the support priorto dropping the composition and rotating the support so as to improvethe compatibility of the composition with respect to the support.

The pre-baking may be performed by, for example, using a hot plate or anoven at 70° C. to 130° C. for from about 0.5 minutes to 15 minutes.

The thickness of the colored curable composition layer formed from thecolored curable composition may be appropriately selected according tothe purpose. In general, the thickness of the colored curablecomposition layer is preferably in the range of from 0.2 μm to 5.0 μm,more preferably from 0.3 μm to 2.5 μm, and most preferably from 0.3 μmto 1.5 μm. The thickness of the colored curable composition layermentioned here refers to a film thickness after pre-baking.

—Step (B)—

In the production method of the color filter of the first aspect of theinvention, subsequently, the colored curable composition layer that hasbeen formed on the support is exposed to light through a mask.

The light or radiation use for the exposure is preferably g-line,h-line, i-line, KrF beam or ArF beam, and particularly preferablyi-line. When i-line is used, the exposure amount is preferably from 100mJ/cm² to 10,000 mJ/cm².

Examples of other usable exposure radiation source include anultrahigh-pressure, high-pressure, medium-pressure or low-pressuremercury lamp, a chemical lamp, a carbon-arc lamp, a xenon lamp, a metalhalide lamp, various visible and ultraviolet laser sources, afluorescent lamp, a tungsten lamp, and sunlight.

(Exposure Step Using Laser Source)

In the exposure step performed with a laser light source, ultravioletlaser beam may be used as a light source. The term Laser is an acronymof Light Amplification by Stimulated Emission of Radiation. Lasers areproduced from a phenomenon of induced emission that occurs in asubstance having a population inversion, and examples of an oscillator,an amplifier or an exiton medium that produces monochromatic lighthaving intensified coherency and directionality by means ofamplification or oscillation of light waves includes crystals, glass,liquids, dyes and gases. From these media, known laser beams having anoscillation Wavelength in an ultraviolet region, such as solid laser,liquid laser, gas laser or semiconductor laser, are obtained. Amongthem, solid laser and gas laser are preferable in view of their outputand oscillation wavelength.

The laser used for exposure with a laser light source is preferablyultraviolet laser having a wavelength of preferably from 300 nm to 380nm, more preferably from 300 nm to 360 nm, since the wavelength of thisrange corresponds to the photosensitive wavelength of a resist (coloredcurable composition).

Specifically, Nd:YAG laser (third harmonic: 355 nm), which is relativelyunexpensive solid laser with a high output, and excimer lasers (XeCl:308 nm, XeF: 353 nm) are preferably used.

The exposure dose with respect to the target (colored curablecomposition) is preferably in the range of from 1 mJ/cm² to 100 mJ/cm²,more preferably from 1 mJ/cm² to 50 mJ/cm². The exposure dose in thisrange is preferable in terms of the productivity of the formed pattern.

The exposure apparatus that can be used in the exposure step using alaser source is not particularly limited, and examples thereof includecommercially available apparatuses such as CALLISTO (trade name,manufactured by V Technology Co., Ltd.), EGIS (trade name, manufacturedby V Technology Co., Ltd.) and DF2200G (trade name, manufactured byDainippon Screen Mfg. Co., Ltd.), and other apparatuses may also bepreferably used.

Light-emitting diodes (LEDs) or laser diodes (LDs) may also be used asan active radiation source. Specifically, when an ultraviolet radiationsource is desired, an ultraviolet LED or an ultraviolet LD may be used.Examples thereof include a violet LED having a main emission spectrum ina wavelength range between 365 nm and 420 nm, which is commerciallyavailable from Nichia Corporation. When a further shorter wavelength isdesired, an LED that emits active radiation centered at a region between300 nm and 370 nm disclosed in U.S. Pat. No. 6,084,250 may be used.Other types of ultraviolet LED are also available, which provideradiation in various ultraviolet ranges. The active radiation sourceparticularly preferred in the invention is UV-LED, and even morepreferably UV-LED having a peak wavelength in a range of from 340 nm to370 nm.

Since ultraviolet lasers exhibit favorable parallelism, pattern exposurecan be performed without a mask by using the same. However, it ispreferred to use a mask during the pattern exposure from the viewpointof further improving the linearity of the pattern.

The exposed colored curable composition layer may be heated with a hotplate or an oven at 70° C. to 180° C. for 0.5 minutes to 15 minutes,prior to the subsequent development treatment.

Further, the exposure may be performed while allowing a nitrogen gas toflow in a chamber, in order to suppress oxidation and discoloration ofthe colorant in the colored curable composition layer.

Subsequently, the exposed colored curable composition layer is developedusing a developer. Thorough these processes, a colored pattern (resistpattern) is formed.

The developer may be a combination of various organic solvents or analkaline aqueous solution, as long as it can dissolve uncured portions(unexposed portions) and does not dissolve cured portions (exposedportions) of the colored curable composition layer. When the developeris an alkaline aqueous solution, the alkali concentration is preferablyadjusted such that the pH of the developer is from 11 to 13, morepreferably from 11.5 to 12.5. In particular, an alkaline aqueoussolution in which the concentration of tetraethylammonium hydroxide isadjusted to 0.001% by mass to 10% by mass, preferably 0.01% by mass to5% by mass, may be suitably used as a developer.

The development time is preferably in the range of from 30 seconds to300 seconds, more preferably from 30 seconds to 120 seconds. Thedevelopment temperature is preferably from 20° C. to 40° C., morepreferably 23° C.

The development may be performed by a puddle system, a shower system, aspray system or the like.

When the development is performed with an alkali aqueous solution, it ispreferable to wash the colored curable composition layer with waterafter the development. The method of washing may be appropriatelyselected according to the purpose. For example, the washing may beperformed by rotating the support such as a silicon wafer substrate at arevolution rate of from 10 rpm to 500 rpm and showering the same withpure water supplied from ejection nozzles positioned above therevolution center.

Thereafter, in the production method of the color filter of the firstaspect of the invention, the colored pattern that has been developed maybe optionally subjected to post-heating and/or post-exposure in order toaccelerate curing of the colored pattern.

—Step (C)—

In particular, in the production method of the color filter of the firstaspect of the invention, color transfer to the adjacent pixels or to theupper and lower layers from the colored curable composition can beeffectively suppressed by performing post-exposure with ultravioletradiation. Color transfer is a problem that occurs when a dye such as aspecific complex is used as a colorant, but this problem can bealleviated by performing post-exposure with ultraviolet radiation.

(Post-Exposure by Ultraviolet Irradiation)

When performing post-exposure with ultraviolet irradiation, it ispreferably performed at an exposure dose [mJ/cm²] that is at least 10times as large as the exposure dose used in the exposure prior to thedevelopment [mJ/cm²].

By exposing the developed colored pattern to ultraviolet light (UVlight) for a certain period of time between the development and the heattreatment at step (D) as mentioned below, occurrence of color transferduring the subsequent heating may be effectively suppressed, and lightfastness may be improved.

As a light source for irradiating ultraviolet light, for example, anultrahigh-pressure mercury lamp, a high-pressure mercury lamp, alow-pressure mercury lamp, a deep UV lamp or the like may be used. Amongthem, a light source that irradiates ultraviolet light including lightat a wavelength of 275 nm or less, in which an irradiation illuminance[mW/cm²] of the light at a wavelength of 275 nm or less is 5% or morewith respect to the integral irradiation illuminance of the light of allwavelengths in ultraviolet light, is preferable. By adjusting theirradiation illuminance of the light at a wavelength of 275 nm or lessin the ultraviolet light to be 5% or more, color transfer to theadjacent pixels or the upper and lower layers can be further suppressed,and light fastness can be further improved.

From these viewpoints, the post-exposure with ultraviolet irradiation ispreferably performed by using a different type of light source from thelight source used in the exposure in the step (B), i.e., bright linesuch as i-line. Specifically, the post-exposure is preferably performedby using a high-pressure mercury lamp, a low-pressure mercury lamp, orthe like. Among them, for the same reasons as mentioned above, theirradiation illuminance [mW/cm²] of light at a wavelength of 275 nm orless is preferably 7% or more with respect to the integral irradiationilluminance of the light of all wavelengths in the ultraviolet light.Further, the upper limit of the irradiation illuminance of the light ata wavelength of 275 nm or less is desirably 25% or less.

The “integral irradiation illuminance” refers to the sum (area) ofilluminances of lights of wavelengths included in the exposure light,which is obtained by drawing a curve when the illuminance at eachspectral wavelength (radiation energy passing through a unit area/unittime; [mW/m²]) is the ordinate and the wavelength [nm] of the light isthe abscissa.

It is preferable that ultraviolet light is irradiated at an irradiationdose [mJ/cm²] of at least 10 times as large as the exposure dose used inthe exposure of the step (B). When the irradiation dose in the step (C)is less than 10 times as large as the exposure dose used in the exposureof the step (B), color transfer between adjacent pixels or to the upperand lower layers may be not prevented, and light fastness may bedeteriorated.

Among them, the irradiation dose of ultraviolet light is preferably from12 times to 200 times, more preferably from 15 times to 100 times, aslarge as the exposure dose used in the exposure of the step (B).

In this case, the integral irradiation illuminance in the irradiatedultraviolet light is preferably 200 mW/cm² or more. When the integralirradiation illuminance is 200 mW/cm² or more, an effect of suppressingcolor transfer between adjacent pixels or to the upper and lower layersand an effect of improving light fastness may be more effectivelyachieved. Among them, the integral irradiation illuminance is preferablyin the range of from 250 mW/cm² to 2,000 mW/cm², more preferably from300 mW/cm² to 1,000 mW/cm².

—Step (D)—

The colored pattern that has been subjected to the post-exposure withultraviolet irradiation as mentioned above is preferably subjected to aheat treatment. By heating (post-baking) the formed colored pattern, thecolored pattern can be further cured.

The heat treatment may be performed by using, for example, a hot plate,various kinds of heaters, an oven or the like.

The temperature for the heat treatment is preferably in the range of100° C. to 300° C., more preferably 150° C. to 250° C. The heating timeis preferably in the range of 30 seconds to 30,000 seconds, morepreferably 60 seconds to 1,000 seconds.

In the production method of the color filter of the first aspect of theinvention, the post-exposure may be performed with g-line, h-line,i-line, KrF, ArF, electron beams or X-rays, instead of performing withultraviolet radiations as mentioned in the step (C).

When the post-exposure is performed by using the light source asmentioned above, the irradiation time is typically in the range of from10 seconds to 180 seconds, preferably from 20 seconds to 120 seconds,more preferably from 30 seconds to 60 seconds.

Alternatively, in the production method of the color filter of the firstaspect of the invention, only the post-heating performed in the step (D)may be performed without performing the post-exposure with ultravioletirradiation in the step (C).

Although either the post-exposure or the post-heating may be performedfirst, it is preferable to perform the post-exposure prior to thepost-heating. This is because deformation of the shape of color patternthat occurs in the post-heating, such as thermal sagging (change of arectangular pattern into a spherical shape) or hemming bottom (reflowingof the lower part of the pattern) of the colored pattern, can besuppressed by promoting the curing of the pattern by performing thepost-exposure.

The thus obtained colored pattern constitutes pixels of the colorfilter.

A color filter having two or more colors of pixels can be obtained byrepeating the processes (A) and (B), and optionally steps (C) and (D),for the number of times corresponding to the number of colors of thepixels.

The step (C) and/or the step (D) may be performed each time after thecompletion of formation, exposure and development of a colored curablecomposition layer of a single color, or may be performed after thecompletion of formation, exposure and development of colored curablecomposition layers of all colors.

The color filter obtained by the production method of the color filterof the first aspect of the invention (the color filter of the firstaspect of the invention), which is produced from the colored curablecomposition of the first aspect of the invention, exhibits excellentlight fastness.

Accordingly, the color filter of the first aspect of the invention maybe used for liquid crystal display devices, solid-state image sensorsincluding CCD image sensors and CMOS image sensors, and camera systemsusing them. Further, the color filter of the first aspect of theinvention is suitably used for solid-state image sensors in which acolored pattern having an extremely small size is formed on a thin filmand a favorable rectangular cross-sectional profile is required, inparticular CCD and CMOS image sensors with a high resolution of morethan 1,000,000 pixels.

The colored curable composition in accordance with the first aspect ofthe invention can be easily washed off with a known cleaning liquid,even when the colored curable composition is attached, for example, tonozzles of an ejection unit, pipings or the inside of a coatingapparatus, or the like. In this case, in order to conduct washing offmore efficiently, a solvent used in the colored curable compositionaccording to the first aspect of the invention is preferably used as acleaning liquid.

Further, cleaning liquids described in JP-A Nos. 7-128867, 7-146562,8-278637, 2000-273370, 2006-85140, 2006-291191, 2007-2101, 2007-2102,2007-281523 and the like are also suitably used as a cleaning liquid forwashing off the colored curable composition according to the firstaspect of the invention.

Among them, alkylene glycol monoalkyl ether carboxylate and alkyleneglycol monoalkyl ether are preferable.

These solvents may be used alone or in a combination of two or morethereof. When two or more solvents are mixed, a mixture of a solventhaving a hydroxyl group and a solvent having no hydroxyl group ispreferably used. The mass ratio of a solvent with a hydroxyl group to asolvent without a hydroxyl group is in the range of from 1/99 to 99/1,preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. Amixed solvent of propylene glycol monomethyl ether acetate (PGMEA) andpropylene glycol monomethyl ether (PGME) in which the mixing ratio asmentioned above is 60/40 is particularly preferable.

In order to enhance the permeability of the cleaning liquid into thecolored curable composition, the cleaning liquid may contain asurfactant as previously mentioned.

<Solid-State Image Sensor>

The solid-state image sensor of the first aspect of the inventionincludes a color filter of the first aspect of the invention. Since acolor filter of the first aspect of the invention exhibits high lightfastness, a solid-state image sensor including the color filter mayprovide excellent color reproducibility.

The configuration of the solid-state image sensor is not particularlylimited as long as it includes the color filter of the first aspect ofthe invention and acts as a solid-state image sensor.

One example of such a configuration includes, on a support, pluralphotodiodes that constitute a light receiving area for a CCD imagesensor or CMOS image sensor (solid-state image sensor) and transferelectrodes made of polysilicon or the like formed on the support, thecolor filter of the first aspect of the invention formed thereon, and amicrolens formed thereon.

Further, in view of preventing discoloration of the colorant, a camerasystem including the color filter of the first aspect of the inventiondesirably includes a camera lens and an IR cut film provides with adichroic-coated cover glass, a microlens or the like, and materialsthereof preferably have an optical property of absorbing part or all ofUV light of 400 nm or less. Further, it is preferable that the camerasystem has a structure in which permeation of oxygen is decreased so asto suppress oxidative discoloration of the coloring material. Forexample, it is preferable that the camera system is partially orcompletely sealed with a nitrogen gas.

<Liquid Crystal Display Device>

The color filter of the first aspect of the invention exhibits excellentlight fastness and has color pixels having a favorable color hue, andthus it is suitable as a color filter for a liquid crystal displaydevice.

A liquid crystal display device having such a color filter can display ahigh quality image.

The definition of display devices and explanation of such displaydevices are described in, for example, “Electronic Display Device (AkioSasaki, Kogyo Chosakai Publishing Co., Ltd., 1990”, “Display Device(Sumiaki Ibuki, Sangyo Tosho Publishing Co., Ltd., 1989)”. Liquidcrystal display devices are described in, for example, “Next GenerationLiquid Crystal Display Techniques (Tatsuo Uchida, Kogyo ChosakaiPublishing Co., Ltd., 1994)”. The liquid crystal display device to whichthe first aspect of the invention is applicable is not particularlylimited, and the first aspect of the invention can be applied to varioustypes of liquid crystal display devices described in, for example, “NextGeneration Liquid Crystal Display Techniques”.

The color filter of the first aspect of the invention is particularlyeffective when it is used in color TFT liquid crystal display devices.Color TFT liquid crystal display devices are described in, for example,“Color TFT Liquid Crystal Display (Kyoritsu Shuppan Co., Ltd., 1996)”.Further, the first aspect of the invention is applicable to liquidcrystal display devices with a wider view angle such as an in-planeswitching (IPS) system or a multi-domain vertical alignment (MVA)system, as well as STN, TN, VA, OCS, FFS, R-OCB and the like.

The color filter of the first aspect of the invention may also beapplied to a color-filter on array (COA) system, which exhibits highbrightness and high definition. In COA liquid crystal display devices,the color filter layer needs to satisfy requirements for an interlayerdielectric film, such as a low dielectric constant and resistance to aremoving liquid, in addition to satisfying ordinary requirements asmentioned above. It is presumed that by selecting the color or thethickness of the colored pixels, in addition to the type of UV laserexposure method, transmissivity of the color filter with respect to UVlaser used as exposure light can be increased and, as a result, it ispossible to increase the curability of colored pixels and produce thesame without causing chipping, peeling or unevenness. Accordingly, inparticular, it is possible to improve the resistance of a colored layerprovided directly or indirectly on a TFT support, and such a color layeris useful for COA liquid crystal display devices. In order to satisfy alow dielectric constant, a resin coating may be provided on the colorfilter layer.

In the colored layer formed by a COA system, in order to electricallyconnect the ITO electrode disposed on the colored layer and the terminalof the driving substrate disposed below the colored layer, anelectrically conductive path, such as a rectangular through hole havinga side length of about 1 μm to 15 μm or a U-shaped depressed area, needsto be formed. The size (the side length) of the electrically conductivepath is preferably 5 μm or less, and according to the first aspect ofthe invention, an electrically conductive path having a size of 5 μm orless may also be formed.

These image display systems are described, for example, on page 43 of“EL, PDP, LCD Display-Latest Trends of Technology and Markets (ResearchStudy Division of Toray Research Center, Inc., 2001)”.

The liquid crystal display device of the first aspect of the inventionincludes, in addition to the color filter of the first aspect of theinvention, various kinds of members such as an electrode substrate, apolarization film, a phase difference film, a back light, a spacer, anda view angle compensation film. The color filter of the first aspect ofthe invention may be applied to liquid crystal display devices includingthese known members.

These members are described, for example, in “'94 Market of LiquidCrystal Display Related Materials And Chemicals (Kentaro Shima, CMCPublishing Co., Ltd., 1994)” and “2003 Current State And Perspective OfLiquid Crystal Related Market (Ryokichi Omote, Fuji Chimera ResearchInstitute, Inc., 2003)”.

Back lights are described, for example, in SID meeting Digest 1380(2005) (A. Konno et al) and Monthly Display, 2005 December, pages 18-24(Hiroyasu Shima) and pages 25-30 (Takaaki Yagi).

When the color filter of the first aspect of the invention is used inliquid crystal display devices, high contrast can be realized whencombined with a known three-wavelength cold-cathode tube. Further, byusing red, green and blue LED light sources (RGB-LED) as a back light,liquid crystal display devices having high brightness, high colorpurity, and favorable color reproducibility can be obtained.

<Second Aspect>

The second aspect of the present invention is a colored curablecomposition containing a phthalocyanine pigment, a dye multimer having apolymerizable group and a group derived from a dipyrromethene dye, apolymerization initiator, a polymerizable compound, and a solvent.

In has been proved that when a colored pattern is formed from a coloredcurable composition that includes a dye containing a dipyrromethenecompound and a phthalocyanine pigment, a phenomenon in which the colorof the colored pattern bleeds into the adjacent layers (also referred toas “color bleeding”) may occur particularly when a heat treatment isperformed to the colored pattern.

The second aspect of the invention has been made in view of the abovecircumstances, and aims to accomplish the following objects.

Specifically, an object of the second aspect of the invention is toprovide a colored curable composition capable of forming a coloredpattern that exhibits suppressed color bleeding.

Another object of the second aspect of the invention is to provide acolor filter that exhibits suppressed color bleeding and a method forproducing the color filter, and a solid-state. image sensor includingthe color filter.

According to the second aspect of the invention, a colored curablecomposition capable of forming a colored pattern that exhibitssuppressed color bleeding can be provided.

Further, according to the second aspect of the invention, a color filterthat exhibits suppressed color bleeding and a method for producing thecolor filter, and a solid-state image sensor including the color filtercan be provided.

<Colored Curable Composition>

First, the colored curable composition of the second aspect of theinvention will be described.

The colored curable composition of the second aspect of the inventionincludes a phthalocyanine pigment, a dye multimer having a polymerizablegroup and a group derived from a dipyrromethene dye, a polymerizationinitiator, a polymerizable compound, and a solvent.

When a colored pattern is formed from a colored curable compositionincluding a dye containing a dipyrromethene compound and aphthalocyanine pigment, a phenomenon in which the color of the coloredpattern bleeds into the adjacent layers or the laminated layers (colorbleeding) may occur when the colored pattern is subjected to a heattreatment. This is believed to be because a dye containing adipyrromethene compound can readily migrate into the adjacent layers orthe laminated layers via a heat treatment.

In this regard, by using a colored curable composition according to thesecond aspect of the invention, occurrence of color bleeding during theformation of the colored pattern can be suppressed.

Although the reason why color bleeding is suppressed is not fullyunderstood, it is believed to be because migration of the colorant tothe adjacent layers or the laminated layers is suppressed as a result ofusing a dye multimer having a polymerizable group and a group derivedfrom a dipyrromethene dye as a colorant containing a dipyrromethenecompound. However, the present invention is not limited to thissupposition.

<Phthalocyanine Pigment>

The phthalocyanine pigment used in the second aspect of the invention isnot particularly limited as long as it is a pigment having aphthalocyanine backbone. The central metal included in thephthalocyanine pigment may be any metal capable of constituting aphthalocyanine backbone, and is not particularly limited. Among them,magnesium, titanium, iron, cobalt, nickel, copper, zinc and aluminum arepreferably used as the central metal.

Specific examples of the phthalocyanine pigment used in the secondaspect of the invention include C.I. Pigment Blue 15, C.I. Pigment Blue15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue15:4, C.I. Pigment Blue 15:5, C.I. Pigment Blue 15:6, C.I. Pigment Blue16, C.I. Pigment Blue 17:1, C.I. Pigment Blue 75, C.I. Pigment Blue 79,C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37,chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, aluminumphthalocyanine oxide and zinc phthalocyanine. Among them, C.I. PigmentBlue 15, C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:1 and C.I. PigmentBlue 15:2 are preferable, and C.I. Pigment Blue 15:6 is particularlypreferable in view of light fastness and tinctorial strength.

The content of the phthalocyanine pigment in the colored curablecomposition used in the second aspect of the invention is preferably inthe range of from 10% by mass to 60% by mass, more preferably from 20%by mass to 60% by mass, and most preferably from 35% by mass to 50% bymass, with respect to the total solid components of the colored curablecomposition.

<Dye Multimer Containing Polymerizable Group and Group Derived fromDipyrromethene Dye>

The colored curable composition of the second aspect of the inventionincludes at least one kind of dye multimer containing a polymerizablegroup and a group derived from a dipyrromethene dye (hereinafter, alsoreferred to as a “polymerizable group-containing dye multimer”). Thepolymerizable group-containing dye multimer functions, for example, as acolorant in the colored curable composition of the second aspect of theinvention.

The polymerizable group-containing dye multimer exhibits a favorablecolor hue and a high absorption coefficient since it is a dye multimercontaining a group derived from a dipyrromethene dye, and the coloredcurable composition of the second aspect of the invention is capable offorming a cured film that exhibits excellent color purity even when itis formed into a thin film.

The polymerizable group-containing dye multimer may include a singletype of dipyrromethene dye-derived group, or may include two or moretypes thereof.

Since the polymerizable group-containing dye multimer has apolymerizable group, the colored curable composition of the secondaspect of the invention is capable of forming a cured film havingexcellent light fastness, heat resistance and solvent resistance,suppressed color bleeding, and favorable pattern formability, even whenit is formed into a thin film.

The polymerizable group-containing dye multimer may include a singletype of polymerizable group, or may include two or more types thereof.

Examples of the polymerizable group include an ethylenically unsaturatedgroup (for example, a methacryl group, an acryl group or a styrylgroup), a cyclic ether group (for example, an epoxy group or an oxetanylgroup), and the like. Among them, an ethylenically unsaturated group ispreferable in view of heat resistance and solvent resistance afterpolymerization.

It is preferable that the polymerizable group-containing dye multimercontains a structural unit having a polymerizable group and a structuralunit having a group derived from a dipyrromethene dye (hereinafter, alsoreferred to as a “structural unit having a dye-derived group”) asrepeating units.

Further, the polymerizable group-containing dye multimer may containother structural units, in addition to a “structural unit having apolymerizable group” and a “structural unit having a dye-derived group”.

In the polymerizable group-containing dye multimer, in view of reducingthe thickness of a color filter, the content of the structural unithaving a dye-derived group is preferably, by mass ratio, in the range offrom 60% by mass to 99% by mass, more preferably from 70% by mass to 97%by mass, and even more preferably from 80% by mass to 95% by mass.

Further, in view of heat resistance and solvent resistance, the contentof the structural unit having a polymerizable group is preferably, bymass ratio, in the range of from 1% by mass to 40% by mass, morepreferably from 3% by mass to 30% by mass, and even more preferably from5% by mass to 20% by mass.

Although the weight average molecular weight of the polymerizablegroup-containing dye multimer (polystyrene-converted value measured by aGPC method) is not particularly limited, it is preferably in the rangeof from 3000 to 50000, more preferably from 5000 to 30000, andparticularly preferably from 7000 to 20000, in view of more effectivelysuppressing color bleeding.

The structural unit having a dye-derived group may be introduced intothe polymerizable group-containing dye multimer by performing, forexample, radical polymerization of a dye compound in which apolymerizable group (for example, an acryloxy group, a methacryloxygroup or a styryl group) is introduced into a dipyrromethene dyebackbone. Alternatively, the structural unit having a dye-derived groupmay be introduced into the polymerizable group-containing dye multimerby allowing a dye compound, in which a group capable of polycondensationor polyaddition reaction is introduced into the dipyrromethene dyebackbone, to react with a multifunctional crosslinking agent.

The structural unit having a polymerizable group may be introduced intothe polymerizable group-containing dye multimer, for example, by thefollowing method.

Specifically, the structural unit having a polymerizable group may beintroduced by copolymerizing the dye compound and a copolymerizationcomponent that does not have a dye backbone (for example, methacrylicacid, acrylic acid or hydroxyethyl methacrylate) to obtain a multimer,and then adding a polymerizable compound having a group capable ofreacting with the structural unit derived from the copolymerizationcomponent (for example, glycidyl methacrylate or methacryloxyethylisocyanate).

Further, a polymerizable group-containing dye multimer may be obtainedby introducing a polymerizable group, which is different from thepolymerizable group responsible for multimerization of a dye compound,into the dipyrromethene dye backbone in the dye compound, and thenpolymerizing the dye compound.

Hereinafter, the dipyrromethene dye, the structural unit having adye-derived group, and the structural unit having a polymerizable groupwill be described in more detail.

(1) Dipyrromethene Dye

Although the dipyrromethene dye is not particularly limited, thedipyrromethene dye represented by the following formula (C) ispreferably used in view of light fastness and heat resistance.

In the formula (C), each of R² to R⁵ independently represents a hydrogenatom or a substituent, R⁷ represents a hydrogen atom, a halogen atom, analkyl group, an aryl group or a heterocyclic group, Ma represents ametal or a metal compound, each of X³ and X⁴ independently represents NR(wherein R represents a hydrogen atom, an alkyl group, an alkenyl group,an aryl group, a heterocyclic group, an acyl group, an alkylsulfonylgroup or an arylsulfonyl group), an oxygen atom or a sulfur atom, Y¹represents NRc (wherein Rc represents a hydrogen atom, an alkyl group,an alkenyl group, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group or an arylsulfonyl group) or a nitrogen atom, Y²represents a nitrogen atom or a carbon atom, each of R⁸ and R⁹independently represents an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an alkoxy group, an aryloxy group, analkylamino group, an arylamino group or a heterocyclic amino group, R⁸and Y¹ may be bonded to each other to form a 5-, 6- or 7-membered ring,R⁹ and Y² may be bonded to each other to form a 5-, 6- or 7-memberedring, X⁵ represents a group capable of being bonded to Ma, and arepresents 0, 1 or 2. Further, the dipyrromethene dye represented by theformula (C) includes a tautomer thereof.

Substituents of the formula (C) will be described in more detail.

Each of R² to R⁵ independently represents a hydrogen atom or asubstituent. Examples of the substituent include a halogen atom (forexample, fluorine, chlorine or bromine), an alkyl group (a linear,branched or cyclic alkyl group having preferably 1 to 48 carbon atoms,more preferably 1 to 24 carbon atoms, such as methyl, ethyl, propyl,isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl,dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl or1-adamantyl), an alkenyl group (an alkenyl group having preferably 2 to48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl,allyl or 3-buten-1-yl), an aryl group (an aryl group having preferably 6to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylor naphthyl), a heterocyclic group (a heterocyclic group havingpreferably 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms,such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl,2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazol-1-yl), asilyl group (a silyl group having preferably 3 to 38 carbon atoms, morepreferably 3 to 18 carbon atoms, such as trimethylsilyl, triethylsilyl,tributylsilyl, t-butyldimethylsilyl or t-hexyldimethylsilyl), a hydroxylgroup, a cyano group, a nitro group, an alkoxy group (an alkoxy grouphaving preferably 1 to 48 carbon atoms, more preferably 1 to 24 carbonatoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy,t-butoxy, dodecyloxy or cycloalkyloxy, for example cyclopentyloxy orcyclohexyloxy), an aryloxy group (an aryloxy group having preferably 6to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such asphenoxy or 1-naphthoxy), a heterocyclic oxy group (a heterocyclic oxygroup having preferably 1 to 32 carbon atoms, more preferably 1 to 18carbon atoms, such as 1-phenyltetrazol-5-oxy or 2-tetrahydropyranyloxy),a silyloxy group (a silyloxy group having preferably 1 to 32 carbonatoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy,t-butyldimethylsilyloxy or diphenylmethylsilyloxy), an acyloxy group (anacyloxy group having preferably 2 to 48 carbon atoms, more preferably 2to 24 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy ordodecanoyloxy), an alkoxycarbonyloxy group (an alkoxycarbonyloxy grouphaving preferably 2 to 48 carbon atoms, more preferably 2 to 24 carbonatoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy orcycloalkyloxycarbonyloxy, for example, cyclohexyloxycarbonyloxy), anaryloxycarbonyloxy group (an aryloxycarbonyloxy group having preferably7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such asphenoxycarbonyloxy), a carbamoyloxy group (a carbamoyloxy group havingpreferably 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms,such as N,N-dimethylcarbamoyloxy, N-butylcarbamoyloxy,N-phenylcarbamoyloxy or N-ethyl-N-phenylcarbamoyloxy), a sulfamoyloxygroup (a sulfamoyloxy group having preferably 0 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms, such as N,N-diethylsulfamoyloxy orN-propylsulfamoyloxy), an alkylsulfonyloxy group (an alkylsulfonyloxygroup having preferably 1 to 38 carbon atoms, more preferably 1 to 24carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy orcyclohexylsulfonyloxy),

an arylsulfonyloxy group (an arylsulfonyloxy group having preferably 6to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such asphenylsulfonyloxy), an acyl group (an acyl group having preferably 1 to48 carbon atoms, more preferably 1 to 24 carbon atoms, such as formyl,acetyl, pivaloyl, benzoyl, tetradecanoyl or cyclohexanoyl), analkoxycarbonyl group (an alkoxycarbonyl group having preferably 2 to 48carbon atoms, more preferably 2 to 24 carbon atoms, such asmethoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl,cyclohexyloxycarbonyl or2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), an aryloxycarbonylgroup (an aryloxycarbonyl group having preferably 7 to 32 carbon atoms,more preferably 7 to 24 carbon atoms, such as phenoxycarbonyl), acarbamoyl group (a carbamoyl group having preferably 1 to 48 carbonatoms, more preferably 1 to 24 carbon atoms, such as carbamoyl,N,N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N,N-dibutylcarbamoyl,N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N-phenylcarbamoyl orN,N-dicyclohexylcarbamoyl), an amino group (an amino group havingpreferably 32 or less carbon atoms, more preferably 24 or less carbonatoms, such as amino, methylamino, N,N-dibutylamino, tetradecylamino,2-ethylhexylamino or cyclohexylamino), an anilino group (an anilinogroup having preferably 6 to 32 carbon atoms, more preferably 6 to 24carbon atoms, such as anilino or N-methylanilino), a heterocyclic aminogroup (a heterocyclic amino group having preferably 1 to 32 carbonatoms, more preferably 1 to 18 carbon atoms, such as 4-pyridylamino), acarbonamido group (a carbonamido group having preferably 2 to 48 carbonatoms, more preferably 2 to 24 carbon atoms, such as acetamido,benzamido, tetradecanamido, pivaloylamido or cyclohexanamido), a ureidogroup (a ureido group having preferably 1 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms, such as ureido, N,N-dimethylureido orN-phenylureido), an imide group (an imide group having preferably 36 orless carbon atoms, more preferably 24 or fewer carbon atoms, such asN-succinimide or N-phthalimide), an alkoxycarbonylamino group (analkoxycarbonylamino group having preferably 2 to 48 carbon atoms, morepreferably 2 to 24 carbon atoms, such as methoxycarbonylamino,ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino orcyclohexyloxycarbonylamino), an aryloxycarbonylamino group (anaryloxycarbonylamino group having preferably 7 to 32 carbon atoms, morepreferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), asulfonamido group (a sulfonamido group having preferably 1 to 48 carbonatoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamido,butanesulfonamido, benzenesulfonamido, hexadecanesulfonamido orcyclohexanesulfonamido), a sulfamoylamino group (a sulfamoylamino grouphaving preferably 1 to 48 carbon atoms, more preferably 1 to 24 carbonatoms, such as N,N-dipropylsulfamoylamino orN-ethyl-N-dodecylsulfamoylamino), an azo group (an azo group havingpreferably 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms,such as phenylazo or 3-pyrazolylazo),

an alkylthio group (an alkylthio group having preferably 1 to 48 carbonatoms, more preferably 1 to 24 carbon atoms, such as methylthio,ethylthio, octylthio or cyclohexylthio), an arylthio group (an arylthiogroup having preferably 6 to 48 carbon atoms, more preferably 6 to 24carbon atoms, such as phenylthio), a heterocyclic thio group (aheterocyclic thio group having preferably 1 to 32 carbon atoms, morepreferably 1 to 18 carbon atoms, such as 2-benzothiazolylthio,2-pyridylthio or 1-phenyltetrazolylthio), an alkylsulfinyl group (analkylsulfinyl group having preferably 1 to 32 carbon atoms, morepreferably 1 to 24 carbon atoms, such as dodecanesulfinyl), anarylsulfinyl group (an arylsulfinyl group having preferably 6 to 32carbon atoms, more preferably 6 to 24 carbon atoms, such asphenylsulfinyl), an alkylsulfonyl group (an alkylsulfonyl group havingpreferably 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms,such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl,isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl,octylsulfonyl or cyclohexylsulfonyl), an arylsulfonyl group (anarylsulfonyl group having preferably 6 to 48 carbon atoms, morepreferably 6 to 24 carbon atoms, such as phenylsulfonyl or1-naphthylsulfonyl), a sulfamoyl group (a sulfamoyl group havingpreferably 32 or less carbon atoms, more preferably 24 or less carbonatoms, such as sulfamoyl, N,N-dipropylsulfamoyl,N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl orN-cyclohexylsulfamoyl), a sulfo group, a phosphonyl group (a phosphonylgroup having preferably 1 to 32 carbon atoms, more preferably 1 to 24carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl orphenylphosphonyl) and a phosphinoylamino group (a phosphinoylamino grouphaving preferably 1 to 32 carbon atoms, more preferably 1 to 24 carbonatoms, such as diethoxyphosphinoylamino or dioctyloxyphosphinoylamino).

When the substituent represented by R² and R⁵ is a substituent that maybe further substituted, it may be further substituted, for example, byany of the above-mentioned substituents. When R² or R⁵ is substituted bytwo or more substituents, these substituents may be the same ordifferent from each other.

Among them, R² and R⁵ preferably represent a cyano group, analkoxycarbonyl group, a carbamoyl group, an acyl group or analkylsulfonyl group, more preferably an alkoxycarbonyl group or acarbamoyl group. Among them, R³ and R⁴ preferably represent asubstituted or unsubstituted alkyl group or a substituted orunsubstituted aryl group, more preferably a substituted or unsubstitutedalkyl group having 1 to 10 carbon atoms, or a substituted orunsubstituted phenyl group.

R⁷ preferably represents a hydrogen atom, a halogen atom, an alkyl group(an alkyl group preferably having 1 to 24 carbon atoms, more preferablyhaving 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, butyl,isopropyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl,cyclohexyl or adamantyl), an aryl group (an aryl group preferably having6 to 24 carbon atoms, more preferably having 6 to 12 carbon atoms, forexample, phenyl or naphthyl), or a heterocyclic group (a heterocyclicgroup preferably having 1 to 24 carbon atoms, more preferably having 1to 12 carbon atoms, for example, 2-thienyl, 4-pyridyl, 2-furyl,2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl orbenzotriazol-1-yl).

Among them, R⁷ preferably represents a hydrogen atom, an alkyl group, anaryl group or a hetero ring, more preferably a hydrogen atom or an alkylgroup, and even more preferably a hydrogen atom.

The alkyl group, aryl group or heterocyclic group of R⁷ may besubstituted, for example, by the substituents represented by R² to R⁵ aspreviously mentioned, and when it is substituted by two or moresubstituents, these substituents may be the same or different from eachother.

In the formula (C), Ma represents a metal atom or a metal compound. Themetal atom or the metal compound may be any metal atom or metal compoundas long as it can form a complex, and examples thereof include adivalent metal atom, a divalent metal oxide, a divalent metal hydroxideand a divalent metal chloride, such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo,Mn, Pb, Cu, Ni, Co and Fe, as well as metal chlorides including AlCl,InCl, FeCl, TiCl₂, SnCl₂, SiCl₂ and GeCl₂, metal oxides including TiOand VO, and metal hydroxides including Si(OH)₂.

In the formula (C), each of X³ and X⁴ independently represents NR, anoxygen atom or a sulfur atom, wherein R represents a hydrogen atom, analkyl group (a linear, branched or cyclic alkyl group having preferably1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such asmethyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl,2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl or1-adamantyl), an alkenyl group (an alkenyl group having preferably 2 to24 carbon atoms, more preferably 2 to 12 carbon atoms, such as vinyl,allyl or 3-buten-1-yl), an aryl group (an aryl group having preferably 6to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylor naphthyl), a heterocyclic group (a heterocyclic group havingpreferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms,such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl,2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazol-1-yl), anacyl group (an acyl group having preferably 1 to 24 carbon atoms, morepreferably 2 to 18 carbon atoms, such as acetyl, pivaloyl, 2-ethylhexyl,benzoyl or cyclohexanoyl), an alkylsulfonyl group (an alkylsulfonylgroup having preferably 1 to 24 carbon atoms, more preferably 1 to 18carbon atoms, such as methylsulfonyl, ethylsulfonyl, isopropylsulfonylor cyclohexylsulfonyl), or an arylsulfonyl group (an arylsulfonyl grouphaving preferably 6 to 24 carbon atoms, more preferably 6 to 18 carbonatoms, such as phenylsulfonyl or naphthylsulfonyl).

The alkyl group, alkenyl group, aryl group, heterocyclic group, acylgroup, alkylsulfonyl group or arylsulfonyl group represented by R may besubstituted by, for example, any of the substituents represented by R²to R⁵ as previously mentioned, and when it is substituted by two or moresubstituents, these substituents may be the same or different from eachother.

In the formula (C), Y¹ represents NRc or a nitrogen atom, and Rc has thesame definitions as that of R for X³ and X⁴, and preferable embodimentsthereof are also the same.

In the formula (C), each of R⁸ and R⁹ independently represents an alkylgroup (a linear, branched or cyclic alkyl group having preferably 1 to36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl,ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl,dodecyl, cyclopropyl, cyclopentyl, cyclohexyl or 1-adamantyl), analkenyl group (an alkenyl group having preferably 2 to 24 carbon atoms,more preferably 2 to 12 carbon atoms, such as vinyl, allyl or3-buten-1-yl), an aryl group (an aryl group having preferably 6 to 36carbon atoms, more preferably 6 to 18 carbon atoms, such as phenyl ornaphthyl), a heterocyclic group (a heterocyclic group having preferably1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl,2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazol-1-yl), analkoxy group (an alkoxy group having preferably 1 to 36 carbon atoms,more preferably 1 to 18 carbon atoms, such as methoxy, ethoxy,propyloxy, butoxy, hexyloxy, 2-ethylhexyloxy, dodecyloxy orcyclohexyloxy), an aryloxy group (an aryloxy group having preferably 6to 24 carbon atoms, more preferably 6 to 18 carbon atoms, such asphenoxy or naphthyloxy), an alkylamino group (an alkylamino group havingpreferably 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms,such as methylamino, ethylamino, propylamino, butylamino, hexylamino,2-ethylhexylamino, isopropylamino, t-butylamino, t-octylamino,cyclohexylamino, N,N-diethylamino, N,N-dipropylamino, N,N-dibutylaminoor N-methyl-N-ethylamino), an arylamino group (an arylamino group havingpreferably 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms,such as phenylamino, naphthylamino, N,N-diphenylamino orN-ethyl-N-phenylamino), or a heterocyclic amino group (a heterocyclicamino group having preferably 1 to 24 carbon atoms, more preferably 1 to12 carbon atoms, such as 2-aminopyrrole, 3-aminopyrazole,2-aminopyridine or 3-aminopyridine).

Among them, R⁸ and R⁹ each preferably represent a substituted orunsubstituted alkyl group or a substituted or unsubstituted aryl group,more preferably a substituted or unsubstituted alkyl group having 1 to15 carbon atoms or a substituted or unsubstituted phenyl group having 6to 15 carbon atoms.

In the formula (C), when the alkyl group, alkenyl group, aryl group,heterocyclic group, alkoxy group, aryloxy group, alkylamino group,arylamino group or heterocyclic amino group represented by R⁸ or R⁹ is agroup that can be further substituted, for example, it may besubstituted by the substituents represented by R² to R⁵ as previouslymentioned, and when it is substituted by two or more substituents, thesesubstituents may be the same or different from each other.

In the formula (C), R⁸ and Y¹ may be bonded to each other to form,together with the carbon atom, a 5-membered ring (for example,cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane,tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran orbenzothiophene), a 6-membered ring (for example, cyclohexane,piperidine, piperazine, morpholine, tetrahydropyran, dioxane,pentamethylenesulfide, dithiane, benzene, piperidine, piperazine,pyridazine, quinoline or quinazoline) or a 7-membered ring (for example,cycloheptane or hexamethyleneimine).

In the formula (C), R⁹ and Y² may be bonded to each other to form,together with the carbon atom, a 5-membered ring (for example,cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane,tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran orbenzothiophene), a 6-membered ring (for example, cyclohexane,piperidine, piperazine, morpholine, tetrahydropyran, dioxane,pentamethylenesulfide, dithiane, benzene, piperidine, piperazine,pyridazine, quinoline or quinazoline) or a 7-membered ring (for example,cycloheptane or hexamethyleneimine).

In the formula (C), when the 5-, 6- or 7-membered ring formed by R⁸ andY¹ or R⁹ and Y² is a ring that can be substituted, it may be substitutedby the substituents represented by R² to R⁵ as previously mentioned, andwhen it is substituted by two or more substituents, these substituentsmay be the same or different from each other.

X⁵ in the formula (C) may be any group as long as it is capable of beingbonded to Ma, and specific examples thereof include water, alcohols (forexample, methanol, ethanol and propanol) and the like, as well as thecompounds described in “Metal Chelates” [1] Takeichi Sakaguchi andKyohei Ueno (1995, Nankodo), “Metal Chelates” [2] (1996), “MetalChelates” [3] (1997), and the like. Among them, water, carboxylic acidcompounds, sulfonic acid compounds and alcohols are preferable, andwater, carboxylic acid compounds and sulfonic acid compounds are morepreferable, in view of production. a represents 0, 1 or 2.

In the compound represented by the formula (C), preferable embodimentsof R² to R⁵ are the same as that of R² to R⁵ as previously described,preferable embodiments of R⁷ are the same as that of R⁷ as previouslydescribed, Ma represents Zn, Cu, Co or VO, each of X³ and X⁴independently represents NR (wherein R represents a hydrogen atom or analkyl group) or an oxygen atom, Y¹ represents NRc (wherein Rc representsa hydrogen atom or an alkyl group) or a nitrogen atom, Y² represents anitrogen atom or a carbon atom, each of R⁸ and R⁹ independentlyrepresent an alkyl group, an aryl group, a heterocyclic group, an alkoxygroup or an alkylamino group, X⁵ represents a group that is bonded viaan oxygen atom, and a represents 0 or 1. R⁸ and Y¹ may be bonded to eachother to form a 5-membered or a 6-membered ring, or R⁹ and Y² may bebonded to each other to form a 5- or 6-membered ring.

In more preferable embodiments of the compound represented by theformula (C), each of R² and R⁵ independently represents analkoxycarbonyl group or a carbamoyl group, each of R³ and R⁴independently represents a substituted or unsubstituted alkyl group or asubstituted or unsubstituted phenyl group, R⁷ represents a hydrogen atomor a methyl group, each of R⁸ and R⁹ independently represents asubstituted or unsubstituted alkyl group or a substituted orunsubstituted phenyl group, X³ and X⁴ each represent an oxygen atom, Y¹represents NRc (wherein Rc represents a hydrogen atom or an alkyl group)or a nitrogen atom, Y² represents a nitrogen atom, Ma represents Zn, andX⁵ represents a carboxylic acid compound or a sulfonic acid compound.

In the formula (C), the position to which the polymerizable groupresponsible for multimerization (formation of a dye multimer) is to beintroduced is not particularly limited, but is preferably any one ormore of R² to R⁵, R⁸, R⁹ and X⁵, more preferably any one or more of R³,R⁴, R⁸ and R⁹, and even more preferably R⁸ and/or R⁹, in view ofsynthesis suitability.

The molar absorption coefficient of the dipyrromethene dye representedby the formula (C) is preferably as high as possible, in view of filmthickness. The maximum absorption wavelength (λmax) is preferably in therange of from 520 nm to 580 nm, more preferably from 530 nm to 570 nm,in view of improving color purity. The maximum absorption wavelength andthe molar absorption coefficient are measured by a spectrophotometer(UV-2400PC, trade name, manufactured by Shimadzu Corporation).

The melting point of the dipyrromethene dye represented by the formula(C) is preferably not too high, in view of solubility.

The method of synthesizing a dipyrromethene dye, the method ofmultimerizing a dye, and the method of introducing a polymerizable groupinto a dye may be selected from those described in JP-A No. 2007-147784,JP-A No. 2008-292970, and the like.

(2) Structural Unit Having Dye-Derived Group

The structural unit having a dye-derived group is preferably astructural unit having a group derived from the above-describedpreferable dyes. Specific examples of the structural unit having adye-derived group are shown below, but the invention is not limitedthereto. Hereinafter, the structural unit having a dye-derived group isalso referred to as a “dye unit”.

(3) Structural Unit Having Polymerizable Group

Examples of the structural unit having a polymerizable group, which isincluded in the polymerizable group-containing dye multimer, include astructural unit obtained by adding a polymerizable compound having agroup that reacts with a structural unit (for example, glycidylmethacrylate or methacryloxyethyl isocyanate), the structural beingderived from a copolymerization component (for example, methacrylicacid, acrylic acid, or hydroxyethyl methacrylate) that has beencopolymerized with a known dye compound.

The polymerizable group in the structural unit having a polymerizablegroup (hereinafter, also referred to as a “polymerizable unit”) is notparticularly limited, and examples thereof include an ethylenicallyunsaturated group (for example, a methacryl group, an acryl group or astyryl group), and a cyclic ether group (for example, an epoxy group oran oxetanyl group). Among them, an ethylenically unsaturated group ispreferable in view of heat resistance and solvent resistance.

Examples of the structural unit having a polymerizable group include thefollowing specific examples. However, the invention is not limitedthereto.

L₁ is more preferably selected from the following linking groups.

In the above linking groups, * represents a position to be linked to—COOM, and ** represents a position to be linked to the dipyrromethenebackbone directly or via any one of R₁ to R₆.

In the formula (2), m represents 1, 2 or 3, preferably 1 or 2, morepreferably 1.

In the formula (2), p represents 1 or 2, preferably 1.

In the formula (2), R₈ represents a hydrogen atom or a methyl group.

In the formula (2), Q represents an oxygen atom or NR₉ (R₉ represents ahydrogen atom, an alkyl group, an alkenyl group, an aryl group, aheterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group).

In the formula (2), L₂ represents a single bond or a (n+1)-valentlinking group.

(4) Other Structural Units

The polymerizable group-containing dye multimer may include a furthercopolymerization component as a structural unit, as long as the effectof the invention is not impaired. When the polymerizablegroup-containing dye multimer is synthesized by radical polymerization,the copolymerization component may be any monomer as long as it is amonomer having at least one ethylene group, and specific examplesthereof include the following monomers.

Examples of the copolymerizable monomer include acrylic acid,α-chloroacrylic acid, α-alkyl acrylic acid (for example, methacrylicacid or α-hydroxymethyl acrylic acid) and salts, esters or amidesderived from acrylic acid (for example, sodium acrylate,tetramethylammonium methacrylate, sodium 2-acrylamido-2-methylpropanesulfonate, sodium 3-acryloyloxy propane sulfonate, acrylamide,methacrylamide, diacetone acrylamide, methyl acrylate, methylmethacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexylmethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate,2-dimethylaminoethyl methacrylate, and benzyl methacrylate), vinylesters (for example, vinyl acetate), acrylonitrile, aromatic vinylcompounds (for example, styrene, p-styrene carboxylic acid, andp-styrene sulfonic acid), vinylidene chloride, vinyl alkyl ether (forexample, vinyl ethyl ether), maleic acid ester, itaconic acid, vinylimidazole, vinyl pyridine, vinyl pyrrolidone, and vinyl carbazole.

When the polymerizable group-containing dye multimer is synthesized bypolycondensation or polyaddition (for example, polyester, polyurea,polyamide or polyamide acid), the copolymerizable monomer may be anymonomer as long as it is a monomer having at least two reactive groups,and examples thereof include alcohols (such as 1,6-hexanediol and2,2-bishydroxymethyl propanoic acid), isocyanates (for example,1,3-tolyl diisocyanate, 2,2-bishydroxymethyl propanoic acid), amines(for example, ethylenediamine and trimethylenediamine) and acidanhydrides.

In view of improving formation suitability of a color pattern, thecopolymerizable monomer is preferably a monomer having an alkali-solublegroup, such as methacrylic acid or acrylic acid.

The content of the alkali-soluble group in the polymerizablegroup-containing dye multimer is preferably in the range of from 1% bymass to 40% by mass, more preferably from 3% by mass to 20% by mass, yetmore preferably from 5% by mass to 15% by mass, in view of forming acolored pattern from a colored curable composition including thepolymerizable group-containing dye multimer.

Hereinafter, in the polymerizable group-containing dye multimer, astructural unit derived from a monomer having an alkali-soluble group isalso referred to as an “alkali-soluble unit”.

(5) Specific Examples of Polymerizable Group-Containing Dye Multimer

In the polymerizable group-containing dye multimer of the second aspectof the invention, the type of the dye unit, the polymerizable unit andthe other structural unit (preferably an alkali-soluble unit), thecombination thereof; and the content of each unit (mass %) are notparticularly limited.

In one preferable embodiment of the combination of the structural units,the dye unit is a structural unit having a group derived from theabove-described preferable dyes, more preferably a structural unithaving a group derived from a dipyrromethene dye represented by theformula (C) or a structural unit having a group derived from an azo dyerepresented by the formula (E); the polymerizable unit is a structuralunit having an ethylenically unsaturated group; and the alkali-solubleunit is a structural unit derived from methacrylic acid or acrylic acid.

Table 1 below shows specific examples of the polymerizablegroup-containing dye multimer of the second aspect of the invention.However, the invention is not limited thereto.

The number of each unit shown in Table 1 below corresponds to the numberof the exemplary compound as preciously described.

TABLE 1 Content Weight Exemplary Polymer- ratio of average compound Dyeizable Alkali-soluble each unit molecular No. unit unit unit (mass %)weight 101 1-1 G-1 Methacrylic acid 85/10/5 6000 102 2-1 G-1 — 90/1013000 103 2-1 G-1 Methacrylic acid 85/10/5 8000 104 2-1 G-1 Acrylic acid85/10/5 4000 105 2-3 G-7 — 90/10 15000 106 2-4 G-1 — 90/10 18000

The column “alkali-soluble unit” in Table 1 shows the monomer used inthe copolymerization.

The content of the polymerizable group-containing dye multimer in thecolored curable composition of the second aspect of the invention mayvary depending on the molecular weight or the molar absorptioncoefficient thereof, but it is preferably in the range of from 5% bymass to 40% by mass, more preferably from 10% by mass to 30% by mass,and particularly preferably from 15% by mass to 25% by mass, withrespect to the total solid components of the composition.

Further, the mass ratio of the phthalocyanine pigment to thepolymerizable group-containing dye multimer (polymerizablegroup-containing dye multimer/phthalocyanine pigment) in the coloredcurable composition of the second aspect of the invention is preferablyin the range of from 0.1 to 3.0, more preferably from 0.1 to 2.0, andparticularly preferably from 0.5 to 1.0.

If the mass ratio (polymerizable group-containing dyemultimer/phthalocyanine pigment) is greater than 0.1, it is possible tomore effectively adjust the color hue properties.

If the mass ratio (polymerizable group-containing dyemultimer/phthalocyanine pigment) is lower than 3.0, it is possible tomore effectively improve the light fastness.

<Dioxazine Pigment>

The colored curable composition of the second aspect of the inventionpreferably further contains a dioxazine pigment. Specific examples,contents and preferable embodiments of the dioxazine pigment are thesame as those according to the first aspect of the invention.

In the colored curable composition of the second aspect of theinvention, the polymerizable group-containing dye multimer may be usedin combination with a colorant having a different structure. Thecolorant having a different structure is not particularly limited andmay be either a dye or a pigment, and known colorants that have beenconventionally used in color filters may be used. For example, thecolorants described in the first aspect may be used.

With respect to the colored curable composition of the second aspect ofthe invention, the polymerizable compound, the polymerization initiatorand the solvent described in the first aspect may be used, andpreferable examples and contents thereof are also the same.

The colored curable composition of the second aspect of the inventionpreferably contains a dispersant. For this purpose, those described inthe first aspect may be used and preferable examples and contents arealso the same.

The colored curable composition of the second aspect of the inventionmay contain other components in addition to the above-mentionedcomponents, as long as the effect of the invention is not impaired. Forthis purpose, those described in the first aspect may be used, andpreferable examples and contents thereof are also the same.

Explanations of the method of preparing a colored curable composition,the color filter and the method for producing the same, the solid-stateimage sensor, and the liquid crystal display device in accordance withthe first aspect of the invention also apply to the second aspect of theinvention.

EXAMPLES

Hereinafter, the present invention will be further described in detailwith reference to the following Examples. However, the invention is notlimited to these Examples. In the following, “part(s)” and “%” refer to“part(s) by mass” and “% by mass”, respectively, unless otherwisespecifically indicated.

First Aspect Examples 1 to 14 and Comparative Examples 1 to 2Preparation of Colored Curable Composition

The following components were mixed and dissolved to give a coloredcomposition 1 (colored curable composition).

-   -   Cyclohexanone: 19.17 parts    -   Resin A (30% PGMEA solution of resin synthesized according to        the following Synthesis Example (benzyl methacrylate/methacrylic        acid copolymer)): 1.057 parts    -   Fluorosurfactant (trade name: CW-1, manufactured by Zeneca, 1%        CyH (cyclohexanone) solution: 1.136 parts    -   Photopolymerization initiator (trade name: CGI-242, manufactured        by BASF Japan): 0.327 parts    -   Polymerizable monomer (trade name: KAYARAD DPHA, manufactured by        Nippon Kayaku Co., Ltd.): 0.8459 parts    -   Dye (Exemplary Compound Ia-5, the above-mentioned specific        complex): 1.09 parts    -   Dispersion of C.I. Pigment Blue 15:6 (PB 15:6) and C.I. Pigment        Violet 23 (PV 23) (solid content concentration: 13.2%, pigment        concentration: 9.4%): 22.615 parts

Synthesis Example of Resin

The resin (benzyl methacrylate/methacrylic acid copolymer) wassynthesized according to the following method.

70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, and 600 g of2-methoxypropanol were placed in a three-necked flask equipped with astirrer, a reflux condenser and a thermometer, and a catalytic amount ofa polymerization initiator (V-65, trade name, manufactured by Wako PureChemical Industries, Ltd.) was added thereto at 65° C. under a nitrogenair flow, and the mixture was stirred for 10 hours. The resulting resinsolution was added dropwise to 20 L of ion-exchanged water whilevigorously stirring, thereby obtaining a white powder. The white powderwas dried at 40° C. under vacuum for 24 hours to give 145 g of a resin(benzyl methacrylate/methacrylic acid copolymer). The resulting resinhad a weight average molecular weight (Mw) of 28,000 and a numberaverage molecular weight (Mn) of 11,000, as measured by GPC,respectively.

The colored composition 1 was prepared such that the mass ratio(dioxazine pigment/dye) (i.e., PV 23/Exemplary Compound Ia-5) was 0.70.

Next, colored compositions 2 to 14 and comparative colored compositions1 and 2 were prepared in a similar manner to the preparation of coloredcomposition 1, except that the type and the amount of the componentswere changed as shown in Table 2.

TABLE 2 Mass ratio (dioxazine Photopolymerization Polymerizable Pigmentdispersion Dye (specific complex) pigment/dye) initiator monomerResin/additive Solvent Colored Dispersion of Exemplary compound a-150.797 Initiator 1 Monomer 1 Resin A PGMEA composition 2 PB15:6 and(0.85) (0.35) (0.85) (1.06) (1130) PV23 (22.615) Colored Dispersion ofExemplary compound a-37 0.618 Initiator 1 Monomer 2 — PGMEA composition3 PB15:6 and (0.8) (0.41) (0.85) (1140) PV23 (22.615) Colored Dispersionof Exemplary compound a-39 0.556 Initiator 1 Monomer 2 — PGMEAcomposition 4 PB15:6 and (0.86) (0.5) (0.85) (1050) PV23 (22.615)Colored Dispersion of Exemplary compound b-3 0.525 Initiator 2 Monomer 3— PGMEA/ composition 5 PB15:6 and (0.88) (0.38) (0.85) Cyclohexane PV23(22.615) (700/350) Colored Dispersion of Exemplary compound b-37 0.691Initiator 3 Monomer 1 — PGMEA/ composition 6 PB15:6 and (0.81) (0.41)(0.75) 2-heptanone PV23 (22.615) (900/210) Colored Dispersion ofExemplary compound 0.399 Initiator Monomer 1 — PGMEA composition 7PB15:6 and a-1/Exemplary compound 1/Initiator 3 (0.78) (1300) PV23(22.615) a-15 (0.4/0.4) (0.2/0.25) Colored Dispersion of Exemplarycompound 0.478 Initiator Monomer 1 — PGMEA composition 8 PB15:6 anda-1/Exemplary compound 1/Initiator 2 (0.9) (1200) PV23 (22.615) b-3(0.6/0.2) (0.3/0.11) Colored Dispersion of Exemplary compound 0.425Initiator Monomer 2 — PGMEA composition 9 PB15:6 and b-3/Exemplarycompound 2/Initiator 3 (0.9) (1150) PV23 (22.615) b-37 (0.25/0.55)(0.18/0.22) Colored Dispersion of Exemplary compound a-1 0.354 Initiator1 Monomer 2 — PGMEA composition 10 PB15:6 and (0.9) (0.4) (0.85) (1050)PV23 (22.615) Colored Dispersion of Exemplary compound a-1 0.671Initiator 1 Monomer 2 — PGMEA composition 11 PB15:6 and (0.95) (0.4)(0.85) (1100) PV23 (22.615) Colored Dispersion of Exemplary compoundIIa-II 0.797 Initiator 1 Monomer 1 Resin A PGMEA composition 12 PB15:6and (0.85) (0.35) (0.85) (1.06) (1130) PV23 (22.615) Colored Dispersionof Exemplary compound 1-2 0.797 Initiator 1 Monomer 1 Resin A PGMEAcomposition 13 PB15:6 and (0.85) (0.35) (0.85) (1.06) (1130) PV23(22.615) Colored Dispersion of Exemplary compound Ia-3 0.797 Initiator 1Monomer 1 Resin A PGMEA composition 14 PB15:6 and (0.85) (0.35) (0.85)(1.06) (1130) PV23 (22.615) Comparative 1 Dispersion of Exemplarycompound a-15 0 Initiator 1 Monomer 1 Resin A PGMEA PB15:6 (22.615)(0.85) (0.35) (0.85) (1.06) (1130) Comparative 2 Dispersion of Exemplarycompound a-37 0 Initiator 1 Monomer 2 — PGMEA PB15:6 (22.615) (0.8)(0.41) (3.37) (1140)

The numerical values in the parenthesis in Table 2 represent the contentof the component (parts by mass).

—Preparation of Single-Color Color Filter and Evaluation of LightFastness—

The colored curable compositions obtained in the above process (coloredcompositions 1 to 14) were applied onto a glass substrate using a spincoater so as to form a film having the thickness after drying of 0.6 μm,and pre-baked at 100° C. for 120 seconds to form a single-color colorfilter for evaluation of light fastness, respectively.

The resulting single-color color filter for evaluation of light fastnesswas exposured to light with a xenon lamp at 100,000 lux for 10 hours(i.e., 1,000,000 lux·h). The color difference (ΔE*ab value) of thesingle-color color filter before and after the exposure with the xenonlamp was measured and used as an index of light fastness. The smallerthe ΔE*ab value is, the more favorable the light fastness is. Theresults are shown in Table 3.

TABLE 3 Light fastness Colored curable composition (ΔE*ab) Example 1Colored composition 1 2.6 Example 2 Colored composition 2 2.4 Example 3Colored composition 3 3.1 Example 4 Colored composition 4 3.5 Example 5Colored composition 5 3.8 Example 6 Colored composition 6 2.8 Example 7Colored composition 7 4.1 Example 8 Colored composition 8 3.6 Example 9Colored composition 9 3.9 Example 10 Colored composition 10 4.0 Example11 Colored composition 11 2.9 Example 12 Colored composition 12 6.1Example 13 Colored composition 13 5.8 Example 14 Colored composition 145.9 Comparative Comparative colored 9.1 Example 1 composition 1Comparative Comparative colored 9.8 Example 1 composition 2

As shown in Table 3, color filters of Examples 1 to 14, which wereproduced using the colored compositions 1 to 14 each containing aphthalocyanine pigment, a dioxazine pigment, a dye, a polymerizationinitiator, a polymerizable compound, and a solvent, exhibited excellentlight fastness.

On the other hand, color filters of Comparative Examples 1 and 2, whichwere produced using comparative colored composition 1 and comparativecolored composition 2, in which a dioxazine pigment was not contained,exhibited poor light fastness.

Examples 2-1 to 2-14 Formation of Blue Color Filter

A 6-inch silicon wafer was subjected to a heat treatment in an oven at200° C. for 30 minutes. A resist liquid, in which the components shownbelow were dissolved, was applied onto the silicon wafer to form a filmhaving the dried film thickness of 1.0 μm, and the film was furtherdried in an oven at 220° C. for 1 hour to form a primer layer. A siliconwafer substrate having a primer layer was thus obtained.

-   -   Propylene glycol monomethyl ether acetate (PGMEA): 19.20 parts    -   Ethyl lactate: 36.67 parts    -   Binder: 41% EL solution of benzyl methacrylate/methacrylic        acid/2-hydroxyethyl methacrylate copolymer: 30.51 parts    -   Dipentaerythritol hexaacrylate: 12.20 parts    -   Polymerization inhibitor (p-methoxyphenol): 0.0061 parts    -   Fluorosurfactant (trade name: CW-1, manufactured by Zeneca) 1%        CyH (cyclohexanone) solution: 0.83 parts    -   Photopolymerization initiator (TAZ-107, trade name, manufactured        by Midori Kagaku Co., Ltd.): 0.586 parts

The above binder (benzyl methacrylate/methacrylic acid/2-hydroxyethylmethacrylate copolymer) was synthesized in accordance with the followingprocess.

Specifically, 53.0 g (0.300 mol) of benzyl methacrylate, 11.7 g (0.090mol) of 2-hydroxyethyl methacrylate, 7.92 g (0.110 mol) of methacrylicacid, and 50 g of propylene glycol monomethylether acetate were placedin a 300-ml four-necked flask and stirred at 80° C. under a nitrogenatmosphere. A solution prepared by dissolving 0.3118 g (1.91×10⁻³ mol)of a thermal polymerization initiator (2,2′-azobisisobutylnitrile (AIBN)in 10 g of propylene glycol monomethylether acetate) was added thereto,and stirred for 6 hours. Subsequently, the supply of nitrogen wasstopped, and a solution of 0.22 g (1.5× mol) of p-methoxyphenoldissolved in 15 g of propylene glycol monomethylether acetate was addedthereto, and the temperature was elevated to 95° C. and stirred for 2hours. A binder (benzyl methacrylate/methacrylic acid/2-hydroxyethylmethacrylate copolymer) was thus obtained. The resulting binder had anacid value of 30 mgKOH/g and a weight average molecular weight of15,000.

The colored compositions used in Examples 1 to 14 were applied onto theprimer layer of the resulting silicon wafer substrate, respectively, anda photocurable coating film (colored curable composition layer) having adried film thickness of 0.6 μm was formed. A heat treatment (pre-baking)was then performed using a hot plate at 100° C. for 120 seconds. Next,the resulting coating film was exposed to light at a wavelength of 365nm through an island pattern mask having the pattern size of 1.2 μmsquare, using an i-line stepper (FPA-3000i5+, trade name, manufacturedby Canon Inc.) while changing the exposure dose by an amount of 100mJ/cm² from 100 mJ/cm² to 2500 mJ/cm². Thereafter, the silicon wafersubstrate with the coating film formed thereon was placed on ahorizontal rotary table of a spin-shower developing machine (trade name:model DW-30, manufactured by Chemitronics Co., Ltd.) and subjected topuddle development at 23° C. for 60 seconds with a developer (CD-2000,trade name, manufactured by Fujifilm Electronic Materials Co., Ltd.),thereby forming a blue pattern on the silicon wafer substrate.

The silicon wafer substrate with a blue pattern formed thereon was fixedon the horizontal rotary table in a vacuum chuck mode, and rinsed withpure water shower supplied from ejection nozzles placed over therotation center while rotating the silicon wafer substrate with arotation apparatus at a revolution rate of 50 rpm. The resultant wasspray-dried, thereby obtaining a color filter.

It was proved that each of the color filter had a blue pattern having aprofile with a favorable rectangular cross-section, indicating that thecolor filter was suitable for solid-state image sensors.

The spectroscopic properties of the colored patterns were measured witha spectrophotometer (MCPD-3000, trade name, manufactured by OtsukaElectronics Co., Ltd.), and the results showed that each color filterexhibited favorable spectroscopic properties as a blue color filter forsolid-state image sensors.

In the above section, examples of forming a blue pattern (color filter)on a silicon wafer substrate were illustrated by way of Example 2-1 toExample 2-14. A three-color color filter can be produced on a siliconwafer on which a device is formed, by forming a blue color filter usingthe colored compositions 1 to 14, a green color filter by a known methodusing a green color resist, and a red color filter by a known methodusing a red color resist, respectively, on a solid-state image sensorsubstrate (a silicon wafer substrate on which an imaging device such asCCD or CMOS has been formed). A solid-state image sensor having athree-color color filter produced by the above method exhibits excellentlight fastness and favorable spectroscopic properties.

Examples 101 to 115 and Comparative Examples 101 to 113 Preparation ofColored Curable Composition (Colored Composition I)

The following components (combination I) were mixed and stirred toprepare a colored composition I.

<Composition of Colored Curable Composition I (Combination I)>

-   -   Dispersed composition I: 1002 parts    -   Dispersed composition II: 100 parts    -   Dye (exemplary compound of the specific complex shown in Table        4): 49 parts    -   Photopolymerizable compound I: 178 parts    -   Photopolymerization initiator I: 43 parts    -   Alkali-soluble resin I: 275 parts    -   Surfactant I: 0.3 parts    -   PGMEA: 1353 parts

—Preparation of Colored Curable Compositions (Colored Compositions II toVII)—

Colored compositions II to VII were prepared in a similar manner as thepreparation of colored composition I, except that combination I waschanged to combination II to combination VII as shown in Table 4 below,respectively.

TABLE 4 Composition of colored compositions I to VII (combination)Combination Combination Combination Combination Combination CombinationCombination I II III IV V VI VII Dispersed 1002 977 912 977 671 1040 715composition I Dispersed 100 196 455 196 135 0 0 composition II Dye 49 4014 40 27 57 39 Photopolymerizable 178 178 178 161 185 178 185 compound IPhotopolymerization 43 43 43 77 89 43 89 initiator II Alkali-solubleresin I 275 263 229 218 345 286 361 Surfactant I 0.3 0.3 0.3 0.3 0.3 0.30.3 PGMEA 1353 1304 1169 1331 1548 1397 1611 (parts by mass)

Details of the components shown in Table 4 are as follows.

-   -   Dispersed composition I: PB 15:6 dispersed composition (solid        content: 20%, PB 15:6 concentration: 12%)    -   Dispersed composition II: PB 15:6/PV 23 dispersed composition        (solid content: 20%, PB 15:6 concentration: 8.57%, PV 23        concentration: 3.43%)    -   Photopolymerizable compound I: Dipentaerythritol        penta/hexaacrylate    -   Alkali-soluble resin I: 40% PGMEA solution of benzyl        methacrylate/methacrylic acid copolymer (molar ratio: 70/30, Mw:        10,000)    -   Surfactant I: MEGAFAC F-781 F (trade name, manufactured by DIC        Corporation)    -   PGMEA: Propylene glycol monomethyl ether acetate

—Evaluation Step II—

The colored curable compositions obtained in the above process (coloredcompositions I to VII) were evaluated in accordance with the followingprocess (Evaluation step I).

Each of the colored curable compositions was applied onto a glasssubstrate having a size of 100 mm×100 mm (trade name: 1737, manufacturedby Corning Inc.) with a spin coater to form a film having the thicknessof 2.3 μm, and the resultant was pre-baked (dried in an oven at 100° C.for 80 seconds). Thereafter, the entire surface of the coating film wasexposed to light at 100 mJ/cm² (illuminance: 20 mW/cm²).

The coating film, which had been exposed to light and developed, wassubjected to a heat treatment (post-baking) in an oven at 220° C. for0.5 hours, thereby obtaining a colored filter substrate (color filter).

The colored filter substrate was exposed to light with a xenon lamp at120,000 lux for 60 hours (i.e., 7,200,000 lux·h). The color difference(ΔE*ab value) of the single-color color filter before and after theexposure with the xenon lamp was measured and used as an index of lightfastness. The smaller the ΔE*ab value is, the more favorable the lightfastness is.

Based on the ΔE*ab value, the light fastness was evaluated according tothe following evaluation criteria. The evaluation results are shown inTable 5 below.

—Evaluation Criteria for Light Fastness—

A: ΔE*ab is less than 3

B: ΔE*ab is from 3 to less than 6

C: ΔE*ab is 6 or greater

—Evaluation Step II—

The colored curable compositions obtained in the above process (coloredcompositions I to VII) were subjected to the following evaluation(Evaluation step II).

The colored curable composition was applied onto a glass substratehaving a size of 100 mm×100 mm (trade name: 1737, manufactured byCorning Inc.) using a spin coater to form a film having a thickness of2.3 μm, and the film was pre-baked (dried in an oven at 100° C. for 80seconds).

Thereafter, the entire surface of the colored curable composition layerformed on the substrate was subjected to pulse irradiation at about 1mJ/cm² using a laser exposure apparatus (EGIS, trade name, manufacturedby V Technology Co., Ltd., third harmonic of YAG laser, wavelength: 355nm, pulse width: 6 nsec) and the pulse irradiation was performed sixtytimes (exposure).

The coating film, which had been exposed as above and developed, wassubjected to a heat treatment (post-baking) in an oven at 220° C. for0.5 hours, thereby producing a colored filter substrate (color filter).

The colored filter substrate was irradiated with a xenon lamp at 120,000lux for 60 hours (corresponding to 7,200,000 lux·h). The colordifference (ΔE*ab value) of the single-color color filter before andafter the irradiation with a xenon lamp was measured and used as anindex of light fastness. The smaller the ΔE*ab value is, the morefavorable the light fastness is.

Based on the measured ΔE*ab value, light fastness was evaluated inaccordance with the same evaluation criteria as that used in theevaluation step I. The evaluation results are shown in Table 5 below.

—Evaluation Step III—

The colored curable compositions obtained in the above process (coloredcompositions I to VII) were subjected to the following evaluation(Evaluation step III).

The colored curable composition was applied onto a glass substratehaving a size of 100 mm×100 mm (trade name: 1737, manufactured byCorning Inc.) using a spin coater to form a film having a thickness of3.5 μm, and the film was pre-baked (dried in an oven at 100° C. for 80seconds).

Thereafter, the entire surface of the colored curable composition layerformed on the substrate was subjected to pulse irradiation at about 1mJ/cm² using a laser exposure apparatus (EGIS, trade name, manufacturedby V Technology Co., Ltd., third harmonic of YAG laser, wavelength: 355nm, pulse width: 6 nsec) and the pulse irradiation was performed sixtytimes (exposure).

The coating film, which had been exposed as above and developed, wassubjected to a heat treatment (post-baking) in an oven at 220° C. for0.5 hours, thereby producing a colored filter substrate (color filter).

The colored filter substrate was exposed to light with a xenon lamp at120,000 lux for 60 hours (i.e., 7,200,000 lux·h). The color difference(ΔE*ab value) of the single-color color filter before and after theirradiation with a xenon lamp was measured and used as an index of lightfastness. The smaller the ΔE*ab value is, the more favorable the lightfastness is.

Based on the measured ΔE*ab value, light fastness was evaluated inaccordance with the same evaluation criteria as that used in theevaluation step I. The evaluation results are shown in Table 5 below.

TABLE 5 Colored Dye compdsition No. (Exemplary Evaluation Lightfastness(Combination No.) compound No.) step ΔE*ab Example 101 I III-48 I BExample 102 II III-48 I A Example 103 III III-48 I A Example 104 IIIII-47 I A Example 105 II III-51 I A Example 106 II III-58 I B Example107 II III-61 I B Example 108 II III-64 I B Example 109 II III-64-2 I AExample 110 IV III-48 II A Example 111 V III-48 III A Example 112 IVIII-47 II A Example 113 V III-47 III A Example 114 IV III-64 II BExample 115 V III-64 III B Comparative Example 101 VI III-48 I CComparative Example 102 VI III-47 I C Comparative Example 103 VI III-51I C Comparative Example 104 VI III-58 I C Comparative Example 105 VIIII-61 I C Comparative Example 106 VI III-64 I C Comparative Example 107VI III-64-2 I C Comparative Example 108 VI III-48 II C ComparativeExample 109 VII III-48 III C Comparative Example 110 VI III-47 II CComparative Example 111 VII III-47 III C Comparative Example 112 VIIII-64 II C Comparative Example 113 VII III-64 III C

As shown in Table 5, color filters of Examples 101 to 115 prepared fromcolored compositions I, II, III, IV and V, containing a phthalocyaninepigment, a dioxazine pigment, a dye, a polymerization initiator, apolymerizable compound and a solvent, exhibited excellent lightfastness.

On the other hand, color filters of Comparative Examples 101 to 113,prepared from colored compositions VI and VII, not containing adioxazine pigment, exhibited poor light fastness.

Second Aspect Synthesis of Exemplary Compound 101 (Dye Multimer)

A dye unit 1-1 (3.45 g), polymerizable unit G-1 (1.55 g), methacrylicacid (0.5 g) and n-dodecanethiol (420 mg) were dissolved in 28.3 ml ofpropylene glycol monomethyl ether acetate (PGMEA), and the mixture wasstirred at 85° C. under nitrogen, and 478 mg of dimethyl2,2′-azobis(2-methylpropionate) were added thereto. Then, 478 mg ofdimethyl 2,2′-azobis(2-methylpropionate) were further added twice withan interval of two hours, and the temperature was elevated to 90° C. andstirred for another 2 hours. After the completion of the reaction, thereaction liquid was added dropwise to 400 ml of acetonitrile. Theresulting crystal was filtered to give an exemplary compound 101 (4.11g).

The above synthesis example relates to the preparation of exemplarycompound 101. However, it is also possible to synthesize other types ofpolymerizable group-containing dye multimer in accordance with a similarmethod from a chemical viewpoint.

Examples 201 to 208 and Comparative Examples 201 and 202 Preparation ofColored Curable Composition

The following components were mixed and dissolved to give a coloredcomposition 1 (colored curable composition).

-   -   Pigment Blue 15:6 dispersion (solid content concentration: 15%,        pigment concentration: 11.54%): 55.47 parts    -   Dye (Exemplary compound 101 of the above-mentioned dye        multimer): 3.20 parts    -   Polymerizable monomer (trade name: KAYARAD DPHA, manufactured by        Nippon Kayaku Co., Ltd.): 3.34 parts    -   Polymerization initiator (trade name: CGI-242, manufactured by        BASF Japan, oxime polymerization initiator): 0.96 parts    -   Resin (30% PGMEA solution of benzyl methacrylate/methacrylic        acid copolymer (Resin A), molar ratio=70:30, weight average        molecular weight: 30,000): 0.53 parts    -   Fluorosurfactant (CW-1, trade name, manufactured by Zeneca, 1%        CyH solution): 0.1 parts    -   Propylene glycol monomethyl ether acetate (PGMEA): 34.79 parts

Next, colored compositions 2 to 10 (colored curable compositions) wereprepared in a similar manner to the preparation of the coloredcomposition 1, except that the type and the amount of the componentswere changed to those as shown in Table 6 below.

TABLE 6 Pigment Polymerization Polymerizable Resin/ dispersion Dyeinitiator compound additive Surfactant Solvent Colored Dispersion ofExemplary compound 101 Initiator 1 Monomer 1 Resin A CW-1 PGMEAcomposition 2 PB15:6 (55.47) (3.20) (0.96) (3.34) (1.06) (0.1) (34.5)Colored Dispersion of Exemplary compound 102 Initiator 1 Monomer 2 —CW-1 PGMEA/ composition 3 PB15:6 (53.8) (3.31) (0.96) (3.37) (0.1)cyclohexanone (20/15.1) Colored Dispersion of Exemplary compound 103Initiator 1 Monomer 2 — CW-1 PGMEA/ composition 4 PB15:6 (54.1) (3.15)(0.89) (3.51) (0.1) 2-heptanone (20/15.1) Colored Dispersion ofExemplary compound 101/ Initiator 2 Monomer 3 — CW-1 PGMEA/ composition5 PB15:6 (55.3) Exemplary compound 103 (0.91) (3.6) (0.1) PGME (1.7/1.7)(20/15.1) Colored Dispersion of Exemplary compound 104 Initiator 3Monomer 1 — CW-1 PGMEA/ composition 6 PB15:6 and PV 23 (3.25) (0.93)(3.26) (0.1) 2-heptanone (54.3) (20/15.1) Colored Dispersion ofExemplary compound 105 Initiator 1/ Monomer 1 — CW-1 PGMEA composition 7PB15:6 (51.5) (3.18) Initiator 3 (3.5) (0.1) (38.3) (0.5/0.5) ColoredDispersion of Exemplary compound 106 Initiator 1/ Monomer 1 — — PGMEAcomposition 8 PB15:6 (52.3) (3.21) Initiator 2 (3.42) (39.6) (0.6/0.4)Colored Dispersion of Comparative dye A (3.20) Initiator 1 Monomer 1Resin A CW-1 PGMEA composition 9 PB15:6 (55.47) (0.96) (3.34) (1.06)(0.1) (34.5) Colored Dispersion of Comparative dye B (3.31) Initiator 1Monomer 2 — CW-1 PGMEA/ composition 10 PB15:6 (53.8) (0.96) (3.37) (0.1)cyclohexanone (20/15.1)

The numerical values in the parenthesis of the components in Table 6represent the proportion (% by mass) of each component in the coloredcomposition.

In Table 6, “PGME” represents propylene glycol monomethyl ether, “PB15:6” represents Pigment Blue 15:6, and “PV 23” represents PigmentViolet 23.

The “PB 15:6 dispersion” used in the colored compositions 2 to 5 and 7to 10 is the same as “PB 15:6 dispersion” used in the coloredcomposition 1.

The “dispersion of PB 15:6 and PV 23” used in the colored composition 6has a mass ratio (PV23/PB15:6) of 8.0/1.0.

The structures of Initiator 1 to Initiator 3, Monomer 1 to Monomer 3,Comparative Dye A and Comparative Dye B in the column“photopolymerization initiator” of Table 6 are shown below.

<Preparation of Single-Color Color Filter and Evaluation of ColorBleeding>

(1) Preparation of Silicon Wafer with Primer Layer

A 6-inch silicon wafer was subjected to a heat treatment in an oven at200° C. for 30 minutes. Then, a primer layer forming solution (CT-4000,trade name, manufactured by Fujifilm Electronic Materials Co., Ltd.) wasapplied onto the silicon wafer to form a layer having a dried thicknessof 1 μm, and further dried on a hot plate at 200° C. for 5 minutes toform a primer layer, whereby a silicon wafer with a primer layer wasobtained.

(2) Application, Exposure and Development of Colored Curable Composition

The colored curable composition (colored compositions 1 to 10) wasapplied onto the primer layer formed on the silicon wafer obtained inthe above step (1), thereby forming a photocurable coating film. A heattreatment (pre-baking) was performed using a hot plate at 100° C. for120 seconds so as to make the dried thickness of the coating film be 0.6μm. Next, the resulting coating film was exposed to light at awavelength of 365 nm through a Bayer pattern mask having a pattern sizeof 10.0 μm square, using an i-line stepper (FPA-3000i5+, trade name,manufactured by Canon Inc.) while changing the exposure amount by 100mJ/cm² from 100 mJ/cm² to 2500 mJ/cm².

Thereafter, the silicon wafer with the exposed coating film was placedon a horizontal rotary table of a spin-shower developing machine (tradename: MODEL DW-30, manufactured by Chemitronics Co., Ltd.) and subjectedto puddle development at 23° C. for 60 seconds with a developer(CD-2000, trade name, manufactured by Fujifilm Electronic Materials Co.,Ltd.) Then, the silicon wafer was rinsed with pure water shower suppliedfrom ejection nozzles placed over the rotation center of the rotarytable while rotating the silicon wafer at a revolution rate of 50 rpm,and then spray-dried to give a colored pattern.

(3) Post-Cure Treatment of Colored Pattern

The resulting colored pattern was exposed to light with a UV irradiationapparatus (trade name: UMA-802-HC552FFAL, manufactured by Ushio Inc.) atan irradiation dose of 350 mW/cm² for 30 seconds at 35° C. After theexposure, the silicon wafer was heated at 200° C. for 300 seconds tocure the colored pattern.

The silicon wafer with a colored pattern (monochromatic blue colorfilter) was thus prepared.

(4) Preparation of Transparent Film Composition Solution

The following components were mixed and dissolved to prepare atransparent film composition solution (CT-1).

-   -   Propylene glycol monomethyl ether acetate (PGMEA): 63.0 parts    -   Ethyl ethoxy propionate (EEP): 27.0 parts    -   Resin (benzyl methacrylate/methacrylic acid, molar ratio=70:30):        4.88 parts    -   KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co.,        Ltd., polymerizable compound): 4.88 parts    -   Polymerization inhibitor (p-methoxyphenol): 0.0001 parts    -   Fluorosurfactant (trade name: F-475, manufactured by DIC        Corporation): 0.01 parts    -   Photopolymerization initiator        (2(O-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octadiene,        manufactured by BASF Japan): 0.23 parts

(5) Application of Transparent Film Composition

The transparent film composition CT-1 prepared in the above step (4) wasapplied to the colored pattern formed on the silicon wafer obtained inthe above step (3). Then, a heat treatment (pre-baking) was performedusing a hot plate at 100° C. for 120 seconds.

(6) Post-Cure Treatment of Transparent Film Composition

The wafer on which the transparent film composition had been applied wasexposed to light using a UV irradiation apparatus (UMA-802-HC552FFAL,trade name, manufactured by Ushio Inc.) at an irradiation dose of 350mW/cm² for 30 seconds at 35° C. Thereafter, the silicon wafer with theexposed coating film was subjected to a heat treatment for 300 secondsat 200° C.

A transparent film was thus formed on the colored pattern formed on thesilicon wafer.

(7) Evaluation

The resulting colored pattern having the size of 10.0 μm square (Bayerpattern), which was protected with a transparent film, was examined withan optical microscope (×500) from directly above the pattern, andwhether or not the dye was bleeding from a pattern edge into thetransparent film was evaluated in accordance with the followingevaluation criteria.

The evaluation results are shown in Table 7 below.

—Evaluation Criteria—

A: color bleeding was not observed, or a region in which color bleedingoccurred was less than 1.0 μm from the pattern edge.

B: color bleeding was observed in a region ranging from 1.0 μm to 5.0 μmfrom the pattern edge.

C: color bleeding was observed in a region exceeding 5.0 μm from thepattern edge.

TABLE 7 Colored curable Color bleeding composition evaluation Example201 Colored composition 1 A Example 202 Colored composition 2 A Example203 Colored composition 3 A Example 204 Colored composition 4 A Example205 Colored composition 5 A Example 206 Colored composition 6 A Example207 Colored composition 7 A Example 208 Colored composition 8 AComparative Colored composition 9 C Example 201 Comparative Coloredcomposition 10 C Example 202

As shown in Table 7, Examples 201 to 208, in which a colored pattern wasformed from colored compositions 1 to 8, containing a phthalocyaninepigment and a dye multimer having a polymerizable group and adipyrromethene dye-derived group, exhibited suppressed color bleeding.On the other hand, in Comparative Examples 201 and 202, in which acolored pattern was formed from colored compositions 9 and 10,containing a dye other than the dye multimer according to the invention,color bleeding reached a significant level.

Although a colored pattern having the size of 10 μm square was used inthe above Examples, color bleeding is also suppressed when a finecolored pattern (for example, having the size of 1.0 μm square) wasused, similarly to the Examples.

In Examples 201 to 208, a blue colored pattern (color filter) was formedon a silicon wafer substrate from colored compositions 1 to 8. However,it is also possible to obtain a three-color color filter by forming ablue color filter using any of colored compositions 201 to 208, a greencolor filter by a known method using a green color resist, and a redcolor filter by a known method using a red color resist, respectively,on a solid-state image sensor substrate (a silicon wafer substrate onwhich an image sensor such as CCD or CMOS is formed). A solid-stateimage sensor including the three-color color filter exhibits suppressedcolor bleeding in a blue color filter, and exhibits excellent colorreproducibility.

All publications, patent applications, and technical standards mentionedin this specification are herein incorporated by reference to the sameextent as if each individual publication, patent application, ortechnical standard was specifically and individually indicated to beincorporated by reference.

1. A colored curable composition comprising a phthalocyanine pigment, adioxazine pigment, a dye, a polymerization initiator, a polymerizablecompound and a solvent.
 2. The colored curable composition according toclaim 1, wherein the dye comprises a complex comprising a compoundrepresented by following formula (I), and a metal atom or a metalcompound:

wherein, in formula (I), each of R¹ to R⁶ independently represents ahydrogen atom or a substituent, and R⁷ represents a hydrogen atom, ahalogen atom, an alkyl group, an aryl group or a heterocyclic group. 3.The colored curable composition according to claim 1, wherein thedioxazine pigment comprises C.I. Pigment Violet
 23. 4. The coloredcurable composition according to claim 1, wherein a mass ratio of thedioxazine pigment to the dye (dioxazine pigment/dye) is from 0.05 to1.50.
 5. The colored curable composition according to claim 2, whereinthe complex comprises a compound represented by following formula (2):

wherein, in formula (2), each of R₂ to R₅ independently represents ahydrogen atom or a substituent; R₇ represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group or a heterocyclic group; each of R₁₀and R₁₁ independently represents an alkyl group, an alkenyl group, anaryl group, a heterocyclic group, an alkoxy group, an aryloxy group, anamino group, an anilino group or a heterocyclic amino group; asubstituent represented by any of R₂ to R₅, R₁₀ or R₁₁ is a divalentlinking group bonded to -L₁- or -L₂-, or a substituent represented byany of R₂ to R₅, R₁₀ or R₁₁ is a single bond and -L₁- or -L₂- directlysubstitutes the dipyrromethene skeleton; Ma represents a metal or ametal compound; X₁ represents a group to neutralize a charge of Ma; rrepresents 0 or 1; each of X₃ and X₄ independently represents NR(Rrepresenting a hydrogen atom, an alkyl group, an alkenyl group, an arylgroup, a heterocyclic group, an acyl group, an alkylsulfonyl group or anarylsulfonyl group), a nitrogen atom, an oxygen atom or a sulfur atom;each of Y₁ and Y₂ independently represents NR(R representing a hydrogenatom, an alkyl group, an alkenyl group, an aryl group, a heterocyclicgroup, an acyl group, an alkylsulfonyl group or an arylsulfonyl group)or an oxygen atom; R₁₀ and Y₁ may be bonded to each other to form afive, six or seven-membered ring; R₁₁ and Y₂ may be bonded to each otherto form a five, six or seven-membered ring; M represents a hydrogenatom, or an organic base or a metal atom to neutralize a charge of —CO₂⁻, or an anion (CO₂M represents CO₂ ⁻); L₁ represents a single bond or a(m+1)-valent linking group; m represents 1, 2 or 3; p represents 1 or 2;R₈ represents a hydrogen atom or a methyl group; Q represents an oxygenatom or NR₉ (R₉ representing a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group or an arylsulfonyl group); L₂ represents a singlebond or an (n+1)-valent linking group; n represents 1, 2 or 3; qrepresents 1 or 2; when p is 2, the two of {(L₁)-(CO₂M)_(m)} may be thesame or different from each other; when q is 2, the two of{(L₂)-(Q-COC(R₈)═CH₂)n} may be the same or different from each other;when m is 2 or 3, the two or three of (CO₂M) may be the same ordifferent from each other; and when n is 2 or 3, the two or three of(Q-COC(R₈)═CH₂) may be the same or different from each other.
 6. Thecolored curable composition according to claim 5, wherein Ma in formula(2) represents Fe, Zn, Co, V═O or Cu.
 7. The colored curable compositionaccording to claim 5, wherein Ma in formula (2) is Zn.
 8. The coloredcurable composition according to claim 1, wherein the polymerizationinitiator comprises an oxime photopolymerization initiator.
 9. A methodof producing a color filter, the method comprising; (A) applying thecolored curable composition according to claim 1 to a support to form acolored curable composition layer; and (B) forming a colored pattern byexposing the colored curable composition layer to light via a mask anddeveloping the exposed colored curable composition layer.
 10. A colorfilter produced by the method of producing a color filter according toclaim
 9. 11. A solid-state image sensor comprising the color filteraccording to claim
 10. 12. A liquid crystal display device comprisingthe color filter according to claim
 10. 13. A colored curablecomposition comprising a phthalocyanine pigment, a dye multimer having apolymerizable group and a group derived from a dipyrromethene dye, apolymerization initiator, a polymerizable compound and a solvent. 14.The colored curable composition according to claim 13, wherein the dyemultimer comprises, as repeating units, a structural unit that includesthe polymerizable group and a structural unit that includes the groupderived from a dipyrromethene dye.
 15. The colored curable compositionaccording to claim 13, wherein the polymerizable group is anethylenically unsaturated group.
 16. The colored curable compositionaccording to claim 13, wherein the dipyrromethene dye comprises adipyrromethene dye represented by following formula (C):

wherein, in formula (C), each of R² to R⁵ independently represents ahydrogen atom or a substituent; R⁷ represents a hydrogen atom, a halogenatom, an alkyl group, an aryl group or a heterocyclic group; Marepresents a metal or a metal compound; each of X³ and X⁴ independentlyrepresents NR(R representing a hydrogen atom, an alkyl group, an alkenylgroup, an aryl group, a heterocyclic group, an acyl group, analkylsulfonyl group or an arylsulfonyl group), an oxygen atom or asulfur atom; Y¹ represents NRc (Rc representing a hydrogen atom, analkyl group, an alkenyl group, an aryl group, a heterocyclic group, anacyl group, an alkylsulfonyl group or an arylsulfonyl group) or anitrogen atom; Y² represents a nitrogen atom or a carbon atom; each ofR⁸ and R⁹ independently represents an alkyl group, an alkenyl group, anaryl group, a heterocyclic group, an alkoxy group, an aryloxy group, analkylamino group, an arylamino group or a heterocyclic amino group); R⁸and Y¹ may be bonded to each other to form a five, six or seven-memberedring; R⁹ and Y² may be bonded to each other to form a five, six orseven-membered ring; X⁵ represents a group capable of being bonded toMa; and a represents 0, 1 or
 2. 17. The colored curable compositionaccording to claim 13, further comprising a dioxazine pigment.
 18. Thecolored curable composition according to claim 17, wherein the dioxazinepigment comprises C.I. Pigment Violet
 23. 19. The colored curablecomposition according to claim 13, wherein the polymerization initiatorcomprises an oxime photopolymerization initiator.
 20. A color filterproduced by using the colored curable composition according to claim 13.21. A method of producing a color filter, the method comprising; (A)applying the colored curable composition according to claim 13 to asupport to form a colored curable composition layer; and (B) forming acolored pattern by exposing the colored curable composition layer tolight via a mask and developing the exposed colored curable compositionlayer.
 22. A solid-state image sensor comprising the color filteraccording to claim 20.